Isoxazoline insecticides

ABSTRACT

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, N-oxides, and salts thereof, 
                         
wherein
         A is a 6-membered aromatic ring containing carbon atoms and 0-3 nitrogen atoms as ring members, said ring optionally substituted with 1-5 substituents independently selected from R 2 ;   R 1  is C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 3 -C 6  cycloalkyl, C 4 -C 7  alkylcycloalkyl or C 4 -C 7  cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from R 21 ;   R 21  is independently H, halogen, C 1 -C 6  alkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 1 -C 6  alkylthio, C 1 -C 6  haloalkylthio, C 1 -C 6  alkylsulfinyl, C 1 -C 6  haloalkylsulfinyl, C 1 -C 6  alkylsulfonyl, C 1 -C 6  haloalkylsulfonyl, CN or NO 2 ; and   Q is as defined in the disclosure.
 
Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the invention.

FIELD OF THE INVENTION

This invention relates to certain isoxazolines, their N-oxides, saltsand compositions suitable for agronomic, nonagronomic and animal healthuses, methods of their use for controlling invertebrate pests such asarthropods in both agronomic and nonagronomic environments, and fortreatment of parasite infections in animals or infestations in thegeneral environment.

BACKGROUND OF THE INVENTION

The control of invertebrate pests is extremely important in achievinghigh crop efficiency. Damage by invertebrate pests to growing and storedagronomic crops can cause significant reduction in productivity andthereby result in increased costs to the consumer. The control ofinvertebrate pests in forestry, greenhouse crops, ornamentals, nurserycrops, stored food and fiber products, livestock, household, turf, woodproducts, and public health is also important. Many products arecommercially available for these purposes, but the need continues fornew compounds that are more effective, less costly, less toxic,environmentally safer or have different sites of action.

The control of animal parasites in animal health is essential,especially in the areas of food production and companion animals.Existing methods of treatment and parasite control are being compromiseddue to growing resistance to many current commercial parasiticides. Thediscovery of more effective ways to control animal parasites istherefore imperative.

PCT Patent Publication WO 05/085216 discloses isoxazoline derivatives ofFormula i as insecticides

wherein, inter alia, each of A¹, A² and A³ are independently C or N; Gis a benzene ring; W is O or S; and X is halogen or C₁-C₆ haloalkyl.

The isoxazolines of the present invention are not disclosed in thispublication.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 including allgeometric and stereoisomers, N-oxides, and salts thereof, andcompositions containing them and their use for controlling invertebratepests:

wherein

-   -   A is a 6-membered aromatic ring containing carbon atoms and 0-3        nitrogen atoms as ring members, said ring optionally substituted        with 1-5 substituents independently selected from R²;

-   -   Y¹—Y²—Y³ is —CH═CH—S—, —CH═CH—O—, —CH═CH—NH—, —CH═N—NH—,        —S—CH═CH—, —O—CH═CH—, —NH—CH═CH— or —NH—N═CH—;    -   Y⁴ is CR⁴ or N;

-   -   each W¹, W², W³, W⁴, W⁵ and W⁶ is independently O or S;    -   L¹ is C₂-C₆ alkylene optionally substituted with one or more        substituents independently selected from R²²;    -   R¹ is C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₄-C₇ alkylcycloalkyl or C₄-C₇ cycloalkylalkyl, each        optionally substituted with one or more substituents        independently selected from R²¹;    -   each R² is independently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl,        C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆        haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl,        C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, CN or NO₂;    -   each R³ and R⁴ is independently H, halogen, C₁-C₆ alkyl, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio,        C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆        alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, CN or NO₂;    -   R⁵ is H; or C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂        cycloalkyl, C₄-C₁₂ alkylcycloalkyl or C₄-C₁₂ cycloalkylalkyl,        each optionally substituted with one or more substituents        independently selected from R²²; or C(═O)R²³, CO₂R²⁴,        C(═O)NR²⁵R²⁶, OR²⁷, SR²⁸, S(═O)R²⁹, SO₂R³⁰, NR³¹R³² or Q¹;    -   R⁶ is H; or C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂        cycloalkyl, C₄-C₁₂ alkylcycloalkyl or C₄-C₁₂ cycloalkylalkyl,        each optionally substituted with one or more substituents        independently selected from R³³; or C(═O)R²³, CO₂R²⁴,        C(═O)NR²⁵R²⁶ or Q¹; or    -   R⁵ and R⁶ are taken together with the nitrogen atom to which        they are attached to form a ring containing as ring members in        addition to the attaching nitrogen atom from 2 to 6 carbon atoms        and optionally one additional ring member selected from the        group consisting of O, N and S(═O)_(u), said ring optionally        substituted with 1 to 4 substituents independently selected from        the group consisting of halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy,        C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆        alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆ alkylsulfonyl,        C₁-C₆ haloalkylsulfonyl, C(═O)R²³, CO₂R²⁴, C(═O)NR²⁵R²⁶; CN and        NO₂;    -   R⁷ is H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₇        alkylcarbonyl or C₂-C₇ alkoxycarbonyl;    -   R⁸ is C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂        cycloalkyl, C₄-C₁₈ alkylcycloalkyl or C₄-C₁₈ cycloalkylalkyl,        each substituted with one or more substituents independently        selected from R³⁴ and optionally substituted with one or more        substituents independently selected from R³⁵; or    -   R⁷ and R⁸ are taken together with the nitrogen atom to which        they are attached to form a ring containing as ring members in        addition to the attaching nitrogen atom from 2 to 6 carbon atoms        and optionally one additional ring member selected from the        group consisting of O, N and S(═O)_(u), said ring optionally        substituted with 1 to 4 substituents independently selected from        the group consisting of halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy,        C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆        alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆ alkylsulfonyl,        C₁-C₆ haloalkylsulfonyl, C(═O)R²³, CO₂R²⁴ and C(═O)NR²⁵R²⁶;    -   each R⁹ and R¹⁸ is independently H; or C₁-C₁₂ alkyl, C₂-C₁₂        alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂ cycloalkyl, C₄-C₁₂        alkylcycloalkyl or C₄-C₁₂ cycloalkylalkyl, each optionally        substituted with one or more substituents independently selected        from R³⁵;    -   R¹⁰ is C₁-C₁₂ alkyl substituted with one or more R³⁵; or CN,        SCN, S(═O)_(u)R³⁷, SO₂NR³⁷R³⁸, N═CR³⁸R³⁹, N═CR³⁸OR³⁹,        NR³⁷C(═O)R³⁸, NR³⁷C(═O)OR³⁸, SiR⁴¹R⁴²R⁴³, CO₂R³⁶; C(═O)R³⁶,        C(═O)NR³⁷R³⁸, C(═S)SR³⁹, C(═S)OR³⁹, C(═S)R³⁸, C(═S)NR³⁷R³⁸,        P(═O)(OR³⁹)₂ or P(═S)(OR³⁹)₂; provided that when R⁹ is H or an        unsubstituted group of C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆        alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl or C₄-C₇        cycloalkylalkyl, then R¹⁰ is CN, SCN, S(═O)_(u)R³⁷, SO₂NR³⁷R³⁸,        N═CR³⁸R³⁹, N═CR³⁸OR³⁹, SiR⁴¹R⁴²R⁴³, CO₂R³⁶, C(═O)R³⁶,        C(═O)NR³⁷R³⁸, C(═S)SR³⁹, C(═S)OR³⁹, C(═S)R³⁸, C(═S)NR³⁷R³⁸,        P(═O)(OR³⁹)₂ or P(═S)(OR³⁹)₂;    -   R¹¹ is H; or C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl,        C₃-C₁₂ cycloalkyl, C₄-C₁₂ alkylcycloalkyl or C₄-C₁₂        cycloalkylalkyl, each optionally substituted with one or more        substituents independently selected from R³⁵; or CN, C(═O)R²³,        CO₂R²⁴, C(═O)NR²⁵R²⁶, OR²⁷, SR²⁸, S(═O)R²⁹, SO₂R³⁰, NR³¹R³²,        C(═S)SR³⁷, C(═S)OR³⁷, C(═S)R³⁷, C(═S)NR³⁷R³⁸, SO₂NR³⁷R³⁸,        NR³⁷C(═O)R³⁸, NR³⁷SO₂R²⁹ or Q¹;    -   R¹² is H; or C₁-C₁₂ alkyl, C₃-C₇ cycloalkyl, C₄-C₁₂        alkylcycloalkyl, C₄-C₁₂ cycloalkylalkyl, each optionally        substituted with one or more substituents independently selected        from R³⁵; or Q¹;    -   R¹³ is H; or C₁-C₁₂ alkyl, C₃-C₇ cycloalkyl, C₄-C₁₂        alkylcycloalkyl or C₄-C₁₂ cycloalkylalkyl, each optionally        substituted with one or more substituents independently selected        from R³⁵; or CN, C(═O)R³⁶, C(═O)OR³⁷, C(═S)SR³⁷, C(═S)OR³⁷,        C(═S)R³⁷, C(═S)NR³⁷R³⁸ or Q¹; or    -   R¹² and R¹³ are taken together with the carbon atom to which        they are attached to form a carbocyclic ring containing as ring        members from 3 to 6 carbon atoms, said ring optionally        substituted with one or more substituents independently selected        from R³⁵;    -   R¹⁴ and R¹⁵ are independently H; or C₁-C₁₂ alkyl, C₂-C₁₂        alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂ cycloalkyl, C₄-C₁₂        alkylcycloalkyl or C₄-C₁₂ cycloalkylalkyl, each optionally        substituted with one or more substituents independently selected        from R³⁵; or CN, C(═O)R²³, CO₂R²⁴, C(═O)NR²⁵R²⁶, OR²⁷, SR²⁸,        S(═O)R²⁹, SO₂R³⁰, NR³¹R³², C(═S)SR³⁷, C(═S)OR³⁷, C(═S)R³⁷,        C(═S)NR³⁷R³⁸, SO₂NR³⁷R³⁸, NR³⁷C(═O)R³⁸, NR³⁷SO₂R²⁹ or Q¹; or    -   R¹⁴ and R¹⁵ are taken together with the nitrogen atom to which        they are attached to form a ring containing as ring members in        addition to the attaching nitrogen atom from 2 to 6 carbon atoms        and optionally one additional ring member selected from the        group consisting of O, N and S(═O)_(u), said ring optionally        substituted with 1 to 4 substituents independently selected from        the group consisting of halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy,        C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆        alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆ alkylsulfonyl,        C₁-C₆ haloalkylsulfonyl, C(═O)R²³, CO₂R²⁴, C(═O)NR²⁵R²⁶, CN and        NO₂; provided that R¹⁴ and R¹⁵ are other than C₁-C₆ alkyl or        C₁-C₆ haloalkyl when R¹¹ is H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆        alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇        cycloalkylalkyl, C₂-C₇ alkylcarbonyl or C₂-C₇ alkoxycarbonyl;    -   each R¹⁶ and R¹⁷ is independently C₁-C₆ alkyl optionally        substituted with one or more substituents independently selected        from R³⁵; or    -   R¹⁶ and R¹⁷ are taken together with the sulfur atom to which        they are attached to form a ring containing as ring members in        addition to the attaching sulfur atom from 3 to 6 carbon atoms,        said ring optionally substituted with one or more substituents        independently selected from R³⁵;    -   R¹⁹ is C₁-C₆ alkyl optionally substituted with one or more        substituents independently selected from R³⁵;    -   R²⁰ is H; or C₁-C₆ alkyl optionally substituted with one or more        substituents independently selected from R³⁵; or CN, C(═O)R²⁴,        CO₂R²⁴ or NO₂;    -   R²¹ is independently H, halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy,        C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆        alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆ alkylsulfonyl,        C₁-C₆ haloalkylsulfonyl, CN or NO₂;    -   each R²², R³³ and R³⁵ is independently H, halogen, C₁-C₆ alkyl,        C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆        haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl,        C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, CN, NO₂, SCN,        C(═O)R³⁷, CO₂R³⁷, C(═S)SR³⁷, C(═S)OR³⁷, C(═S)R³⁷, C(═O)NR³⁷R³⁸,        C(═S)NR³⁷R³⁸, SO₂NR³⁷R³⁸, NR³⁷R³⁸, SiR⁴¹R⁴²R⁴³ or Q¹;    -   each R²³, R²⁵, R²⁶, R²⁷, R²⁸, R³¹ and R³² is independently H; or        C₁-C₁₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₉ cycloalkyl,        C₄-C₁₀ alkylcycloalkyl or C₄-C₁₀ cycloalkylalkyl, each        optionally substituted with one or more substituents        independently selected from R³⁵; or Q¹;    -   each R²⁴, R²⁹ and R³⁰ is independently H; or C₁-C₁₈ alkyl, C₂-C₈        alkenyl, C₂-C₈ alkynyl, C₃-C₉ cycloalkyl, C₄-C₁₀ alkylcycloalkyl        or C₄-C₁₀ cycloalkylalkyl, each optionally substituted with one        or more substituents independently selected from R³⁵; or Q¹;    -   R³⁴ is OR³⁶, OC(═O)R³⁷, OC(═O)NR³⁷R³⁸, OCO₂R³⁷, OSO₂R³⁹, SH,        SR³⁶, S(═O)R³⁶, SO₂R³⁶, SO₂NR³⁷R³⁸, NR³⁶R³⁷, N═CR³⁷R⁴⁰;        N═CR⁴⁰OR³⁷, NR³⁷C(═O)R³⁸, SCN, SiR⁴¹R⁴²R⁴³; CO₂H, CO₂R⁴⁶,        C(═O)R⁴⁶, C(═S)SR⁴⁰, C(═S)OR⁴⁰, C(═O)SR⁴⁰, C(═S)R³⁷,        C(═S)NR³⁷R³⁸, P(═O)(OR³⁷)₂ or P(═S)(OR³⁷)₂;    -   R³⁶ is Q¹; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₇        alkylcarbonyl or C₂-C₇ alkoxycarbonyl, each substituted with one        or more substituents independently selected from halogen, CN,        NO₂, OR⁴⁴, SR⁴⁴, S(═O)R⁴⁴, SO₂R⁴⁴; CO₂R⁴⁴ and C(═O)NR⁴⁴R⁴⁵;    -   each R³⁷ and R³⁸ is independently H; or Q¹; or C₁-C₆ alkyl,        C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₄-C₇        alkylcycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₇ alkylcarbonyl or        C₂-C₇ alkoxycarbonyl, each optionally substituted with one of        more substituents independently selected from the group        consisting of halogen, CN, NO₂, OR⁴⁴, SR⁴⁴, S(═O)R⁴⁴; SO₂R⁴⁴,        CO₂R⁴⁴, C(═O)NR⁴⁴R⁴⁵ and Q¹;    -   R³⁹ is Q¹; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₇        alkylcarbonyl or C₂-C₇ alkoxycarbonyl, each optionally        substituted with one or more substituents independently selected        from the group consisting of halogen, CN, NO₂, OR⁴⁴, SR⁴⁴,        S(═O)R⁴⁴, SO₂R⁴⁴, CO₂R⁴⁴, C(═O)NR⁴⁴R⁴⁵ and Q¹;    -   R⁴⁰ is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₇        alkylcarbonyl, C₂-C₇ alkoxycarbonyl or a phenyl ring, each        optionally substituted with one of more substituents        independently selected from the group consisting of halogen,        C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, CN and NO₂;    -   each R⁴¹, R⁴² and R⁴³ is independently C₁-C₆ alkyl, C₂-C₆        alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl,        C₄-C₇ cycloalkylalkyl or a phenyl ring, each optionally        substituted with one of more substituents selected from the        group consisting of halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ alkylsulfinyl,        C₁-C₆ alkylsulfonyl, CN and NO₂;    -   each R⁴⁴ and R⁴⁵ is independently H; or C₁-C₆ alkyl, C₂-C₆        alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl        or C₄-C₇ cycloalkylalkyl, each optionally substituted with one        of more substituents selected from R³⁵; or Q¹;    -   R⁴⁶ is Q¹; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₇        alkylcarbonyl or C₂-C₇ alkoxycarbonyl, each substituted with one        or more substituents selected from CN, NO₂, OR⁴⁴, SR⁴⁴,        S(═O)R⁴⁴, SO₂R⁴⁴, CO₂R⁴⁴ and C(═O)NR⁴⁴R⁴⁵;    -   each Q¹ is a 3- to 10-membered ring or 7- to 10-membered        bicyclic ring system containing as ring members from 2 to 10        carbon atoms and from 0 to 5 heteroatoms selected from the group        consisting of carbon, sulfur and nitrogen atoms, of which up to        two of the carbon or sulfur atoms are present as C(═O), S(═O) or        SO₂, said ring or ring system optionally substituted with one or        more substituents independently selected from R²;

m is an integer from 0 to 5;

n is an integer from 0 to 4;

q is 0 or 1; and

u is 0, 1 or 2.

This invention also provides a composition comprising a compound ofFormula 1, an N-oxide or a salt thereof, and at least one additionalcomponent selected from the group consisting of surfactants, soliddiluents and liquid diluents. In one embodiment, this invention alsoprovides a composition for controlling an invertebrate pest comprising abiologically effective amount of a compound of Formula 1, an N-oxide ora salt thereof, and at least one additional component selected from thegroup consisting of surfactants, solid diluents and liquid diluents,said composition optionally further comprising a biologically effectiveamount of at least one additional biologically active compound or agent.

This invention further provides a spray composition for controlling aninvertebrate pest comprising a biologically effective amount of acompound of Formula 1, an N-oxide or a salt thereof, or the compositiondescribed above, and a propellant. This invention also provides a baitcomposition for controlling an invertebrate pest comprising abiologically effective amount of a compound of Formula 1, an N-oxide ora salt thereof, or the compositions described in the embodiments above,one or more food materials, optionally an attractant, and optionally ahumectant.

This invention further provides a trap device for controlling aninvertebrate pest comprising said bait composition and a housing adaptedto receive said bait composition, wherein the housing has at least oneopening sized to permit the invertebrate pest to pass through theopening so the invertebrate pest can gain access to said baitcomposition from a location outside the housing, and wherein the housingis further adapted to be placed in or near a locus of potential or knownactivity for the invertebrate pest.

This invention provides a method for controlling an invertebrate pestcomprising contacting the invertebrate pest or its environment with abiologically effective amount of a compound of Formula 1, an N-oxide ora salt thereof, (e.g., as a composition described herein). Thisinvention also relates to such method wherein the invertebrate pest orits environment is contacted with a composition comprising abiologically effective amount of a compound of Formula 1, an N-oxide ora salt thereof, and at least one additional component selected from thegroup consisting of surfactants, solid diluents and liquid diluents,said composition optionally further comprising a biologically effectiveamount of at least one additional biologically active compound or agent.

This invention also provides a method for protecting a seed from aninvertebrate pest comprising contacting the seed with a biologicallyeffective amount of a compound of Formula 1, an N-oxide or a saltthereof, (e.g., as a composition described herein). This invention alsorelates to the treated seed.

This invention further provides a method for protecting an animal froman invertebrate parasitic pest comprising administering to the animal aparasiticidally effective amount of a compound of Formula 1, an N-oxideor a salt thereof, (e.g., as a composition described herein). Thisinvention further provides a method for treating, preventing, inhibitingand/or killing ecto- and/or endoparasites comprising administering toand/or on the animal a parasiticidally effective amount of a compound ofFormula 1 (e.g., as a composition described herein). This invention alsorelates to such method wherein a parasiticidally effective amount of acompound of Formula 1 (e.g., as a composition described herein) isadministered to the environment (e.g., a stall or blanket) in which ananimal resides.

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains” or “containing,” or any othervariation thereof, are intended to cover a non-exclusive inclusion. Forexample, a composition, a mixture, process, method, article, orapparatus that comprises a list of elements is not necessarily limitedto only those elements but may include other elements not expresslylisted or inherent to such composition, mixture, process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As referred to in this disclosure, the term “invertebrate pest” includesarthropods, gastropods and nematodes of economic importance as pests.The term “arthropod” includes insects, mites, spiders, scorpions,centipedes, millipedes, pill bugs and symphylans. The term “gastropod”includes snails, slugs and other Stylommatophora. The term “nematode”includes all of the helminths, such as roundworms, heartworms, andphytophagous nematodes (Nematoda), flukes (Tematoda), Acanthocephala,and tapeworms (Cestoda).

In the context of this disclosure “invertebrate pest control” meansinhibition of invertebrate pest development (including mortality,feeding reduction, and/or mating disruption), and related expressionsare defined analogously.

The term “agronomic” refers to the production of field crops such as forfood and fiber and includes the growth of corn, soybeans and otherlegumes, rice, cereal (e.g., wheat, oats, barley, rye, rice, maize),leafy vegetables (e.g., lettuce, cabbage, and other cole crops),fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers andcucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g.,pome, stone and citrus), small fruit (berries, cherries) and otherspecialty crops (e.g., canola, sunflower, olives). The term“nonagronomic” refers to other than field crops, such as horticulturalcrops (e.g., greenhouse, nursery or ornamental plants not grown in afield), residential, agricultural, commercial and industrial structures,turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.),wood products, stored product, agro-forestry and vegetation management,public health (i.e. human) and animal health (e.g., domesticated animalssuch as pets, livestock and poultry, undomesticated animals such aswildlife) applications.

The term “nonagronomic” refers to other than field crops, such ashorticultural crops (e.g., greenhouse, nursery or ornamental plants notgrown in a field), residential, agricultural, commercial and industrialstructures, turf (e.g., sod farm, pasture, golf course, lawn, sportsfield, etc.), wood products, stored product, agro-forestry andvegetation management, public health (i.e. human) and animal health(e.g., domesticated animals such as pets, livestock and poultry,undomesticated animals such as wildlife) applications.

Nonagronomic applications include protecting an animal from aninvertebrate parasitic pest by administering a parasiticidally effective(i.e. biologically effective) amount of a compound of the invention,typically in the form of a composition formulated for veterinary use, tothe animal to be protected. As referred to in the present disclosure andclaims, the terms “parasiticidal” and “parasiticidally” refers toobservable effects on an invertebrate parasite pest to provideprotection of an animal from the pest. Parasiticidal effects typicallyrelate to diminishing the occurrence or activity of the targetinvertebrate parasitic pest. Such effects on the pest include necrosis,death, retarded growth, diminished mobility or lessened ability toremain on or in the host animal, reduced feeding and inhibition ofreproduction. These effects on invertebrate parasite pests providecontrol (including prevention, reduction or elimination) of parasiticinfestation or infection of the animal.

A parasite “infestation” refers to the presence of parasites in numbersthat pose a risk to humans or animals. The infestation can be in theenvironment (e.g., in human or animal housing, bedding, and surroundingproperty or structures), on agricultural crops or other types of plants,or on the skin or fur of an animal. When the infestation is within ananimal (e.g., in the blood or other internal tissues), the terminfestation is also intended to be synonymous with the term “infection”as that term is generally understood in the art, unless otherwisestated.

In the present disclosure and claims, the radical “SO₂” means sulfonyl,“CN” means cyano, and “NO₂” means nitro.

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl, such as, methyl, ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl”includes straight-chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.“Alkenyl” also includes polyenes such as 1,2-propadienyl and2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynessuch as ethynyl, 1-propynyl, 2-propynyl and the different butynyl,pentynyl and hexynyl isomers. “Alkynyl” can also include moietiescomprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkylene”denotes a straight-chain or branched alkanediyl. Examples of “alkylene”include CH₂, CH₂CH₂, CH(CH₃), CH₂CH₂CH₂, CH₂CH(CH₃) and the differentbutylene isomers.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy,isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.“Alkylthio” includes branched or straight-chain alkylthio moieties suchas methylthio, ethylthio, and the different propylthio, butylthio,pentylthio and hexylthio isomers. “Alkylsulfinyl” includes bothenantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl”include CH₃S(═O)—, CH₃CH₂S(═O)—, CH₃CH₂CH₂S(═O)—, (CH₃)₂CHS(═O)— and thedifferent butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.Examples of “alkylsulfonyl” include CH₃SO₂—, CH₃CH₂SO₂—, CH₃CH₂CH₂SO₂—,(CH₃)₂CHSO₂—, and the different butylsulfonyl, pentylsulfonyl andhexylsulfonyl isomers.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyland cyclohexyl. The term “alkylcycloalkyl” denotes alkyl substitution ona cycloalkyl moiety and includes, for example, ethylcyclopropyl,i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term“cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety.Examples of “cycloalkylalkyl” include cyclopropylmethyl,cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chainor branched alkyl groups.

The term “halogen”, either alone or in compound words such as“haloalkyl”, or when used in descriptions such as “alkyl substitutedwith halogen” includes fluorine, chlorine, bromine or iodine. Further,when used in compound words such as “haloalkyl”, or when used indescriptions such as “alkyl substituted with halogen” said alkyl may bepartially or fully substituted with halogen atoms which may be the sameor different. Examples of “haloalkyl” or “alkyl substituted withhalogen” include F₃C—, ClCH₂—, CF₃CH₂— and CF₃CCl₂—. The terms“haloalkoxy” and “haloalkylthio” and the like, are defined analogouslyto the term “haloalkyl”. Examples of “haloalkoxy” include CF₃O—,CCl₃CH₂O—, HCF₂CH₂CH₂O— and CF₃CH₂O—. Examples of “haloalkylthio”include CCl₃S—, CF₃S—, CCl₃CH₂S— and ClCH₂CH₂CH₂S—. Examples of“haloalkylsulfinyl” include CF₃S(═O)—, CCl₃S(═O)—, CF₃CH₂S(═O)— andCF₃CF₂S(═O)—. Examples of “haloalkylsulfonyl” include CF₃SO₂—, CCl₃SO₂—,CF₃CH₂SO₂— and CF₃CF₂SO₂—.

“Alkylcarbonyl” denotes a straight-chain or branched alkyl moietiesbonded to a C(═O) moiety. Examples of “alkylcarbonyl” include CH₃C(═O)—,CH₃CH₂CH₂C(═O)— and (CH₃)₂CHC(═O)—. Examples of “alkoxycarbonyl” includeCH₃OC(═O)—, CH₃CH₂OC(═O)—, CH₃CH₂CH₂OC(═O)—, (CH₃)₂CHOC(═O)— and thedifferent butoxy- or pentoxycarbonyl isomers.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 18. Forexample, C₁-C₄ alkylsulfonyl designates methylsulfonyl throughbutylsulfonyl.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can exceed 1, saidsubstituents (when they exceed 1) are independently selected from thegroup of defined substituents, e.g., (R³)_(m) or (R⁴)_(n), m is 0, 1, 2,3, 4 or 5 and n is 0, 1, 2, 3 or 4. As (R³)_(m) or (R⁴) _(n) areoptional substituents on bicyclic rings, Q-A and Q-B respectively, eachmay substitute any available carbon or nitrogen ring member(s) of thebicyclic ring. For example, when Q is Q-A and Y¹—Y²—Y³ is —CH═CH—S—,then the (R³)_(m) substituents can also be attached to the two availablecarbon atoms of the —CH═CH—S— moiety (e.g., —C(R³)═CH—S—, —CH═C(R³)—S—or —C(R³)═C(R³)—S—. When a group contains a substituent which can behydrogen, for example R³ or R⁴, then when this substituent is taken ashydrogen, it is recognized that this is equivalent to said group beingunsubstituted. When a variable group is shown to be optionally attachedto a position, for example (R³)_(m) wherein m may be 0, then hydrogenmay be at the position even if not recited in the variable groupdefinition. When one or more positions on a group are said to be “notsubstituted” or “unsubstituted”, then hydrogen atoms are attached totake up any free valency.

The orientation of the Y¹—Y²—Y³ substitutents is as depicted in Q-A. Forexample, when Y¹—Y²—Y³ is —CH═CH—S—, then Y¹ is CH, Y² is CH and Y³ isS.

The attachment point of a substituent to a structure is represented by awavy line bisecting the bond joining the substituent to the remainder ofthe structure. For example, a benzyl substituent can be represented as

Unless otherwise indicated, a “ring” or “ring system” as a component ofFormula 1 (e.g., substituent A or Q¹) is carbocyclic or heterocyclic.The term “ring system” denotes two or more fused rings. The term“bicyclic ring system” denotes a ring system consisting of two fusedrings, in which either ring can be saturated, partially unsaturated, orfully unsaturated unless otherwise indicated. The term “ring member”refers to an atom or other moiety (e.g., C(═O), C(═S), S(═O) or SO₂)forming the backbone of a ring or ring system.

The terms “carbocyclic ring” or “carbocyclic ring system” denote a ringor ring system wherein the atoms forming the ring backbone are selectedonly from carbon. Unless otherwise indicated, a carbocyclic ring can bea saturated, partially unsaturated, or fully unsaturated ring. When afully unsaturated carbocyclic ring satisfies Hückel's rule, then saidring is also called an “aromatic ring”. “Saturated carbocyclic” refersto a ring having a backbone consisting of carbon atoms linked to oneanother by single bonds; unless otherwise specified, the remainingcarbon valences are occupied by hydrogen atoms.

The terms “heterocyclic ring”, “heterocycle” or “heterocyclic ringsystem” denote a ring or ring system in which at least one atom formingthe ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur.Typically a heterocyclic ring contains no more than 4 nitrogens, no morethan 2 oxygens and no more than 2 sulfurs. Unless otherwise indicated, aheterocyclic ring can be a saturated, partially unsaturated, or fullyunsaturated ring. When a fully unsaturated heterocyclic ring satisfiesHückel's rule, then said ring is also called a “heteroaromatic ring” or“aromatic heterocyclic ring”. Unless otherwise indicated, heterocyclicrings and ring systems can be attached through any available carbon ornitrogen by replacement of a hydrogen on said carbon or nitrogen.

“Aromatic” indicates that each of the ring atoms is essentially in thesame plane and has a p-orbital perpendicular to the ring plane, and inwhich (4n+2)π electrons, where n is a positive integer, are associatedwith the ring to comply with Hückel's rule. The term “aromatic ringsystem” denotes a carbocyclic or heterocyclic ring system in which atleast one ring of the ring system is aromatic. The term “aromaticcarbocyclic ring system” denotes a carbocyclic ring system in which atleast one ring of the ring system is aromatic. The term “aromaticheterocyclic ring system” denotes a heterocyclic ring system in which atleast one ring of the ring system is aromatic. The term “nonaromaticring system” denotes a carbocyclic or heterocyclic ring system that maybe fully saturated, as well as partially or fully unsaturated, providedthat none of the rings in the ring system are aromatic. The term“nonaromatic carbocyclic ring system” denotes a carbocyclic ring inwhich no ring in the ring system is aromatic. The term “nonaromaticheterocyclic ring system” denotes a heterocyclic ring system in which noring in the ring system is aromatic.

As is generally known in the art, the chemical name “pyridyl” issynonymous with “pyridinyl”.

The term “optionally substituted” is used herein interchangeably withthe phrase “substituted or unsubstituted” or with the term“(un)substituted”. Unless otherwise indicated, an optionally substitutedgroup may have a substituent at each substitutable position of thegroup, and each substitution is independent of the other. An optionallysubstituted group also may have no substituents. Therefore the phrase“optionally substituted with one or more substituents” means that thenumber of substituents may vary from zero up to the number of availablepositions for substitution. Similarly the phrase “optionally substitutedwith 1-5 substituents” means that the number of substituents may varyfrom zero up to the number of available position but not exceeding 5.

As already defined, Q¹ is a 3- to 10-membered ring or 7- or 10-memberedbicyclic ring system containing as ring members from 2 to 10 carbonatoms and from 0 to 5 heteroatoms selected from the group consisting ofcarbon, sulfur and nitrogen atoms, of which up to two of the carbon orsulfur atoms are present as C(═O), S(═O) or SO₂, said ring or ringsystem optionally substituted with one or more substituentsindependently selected from R². Therefore the ring or bicyclic ringsystem of Q¹ may be saturated, partially saturated or fully unsaturated(including aromatic if Hückel's rule is satisfied). Furthermore the ringor bicyclic ring system may contain only carbon atoms as ring members(i.e. carbocyclic) or a combination of carbon atoms and heteroatoms(i.e. heterocyclic). In particular, the ring members of Q¹ may includeup to 5 heteroatoms selected from C, S and N as ring members. Thepossible number of heteroatoms is limited by the number of ring membersin the ring or ring system. Up to two of the carbon or sulfur atom ringmembers (including combinations thereof) may be present as C(═O), S(═O)or SO₂ (including combinations thereof).

As defined above, A is a 6-membered aromatic ring containing carbonatoms and 0-3 nitrogen atoms as ring members, said ring optionallysubstituted with 1-5 substituents independently selected from R².Examples of these rings optionally substituted by 1 to 5 substituentsinclude the rings A-1 through A-14 illustrated in Exhibit 1 whereinR^(v) is any substituent as defined in the Summary of the Invention forA (i.e. R²) and r is an integer from 0 to 5, limited by the number ofavailable positions on each A group.

Exhibit 1

When Q¹ is a nitrogen-containing heterocyclic ring or ring system, itmay be attached to the remainder of Formula 1 though any availablecarbon or nitrogen ring atom, unless otherwise described. As notedabove, Q¹ can be (among others) phenyl optionally substituted with oneor more substituents selected from a group of substituents as defined inthe Summary of Invention. An example of phenyl optionally substitutedwith one to five substituents is the ring illustrated as U-1 in Exhibit1, wherein R^(v) is R² as defined in the Summary of the Invention for Q¹and r is an integer from 0 to 5.

As noted above, Q¹ can be (among others) a 5- or 6-membered heterocyclicring, which may be saturated or unsaturated, optionally substituted withone or more substituents selected from a group of substituents asdefined in the Summary of Invention. Examples of a 5- or 6-memberedaromatice unsaturated heterocyclic ring optionally substituted with oneor more substituents include the rings U-2 through U-61 illustrated inExhibit 2 wherein R^(v) is any substituent as defined in the Summary ofthe Invention for Q¹ (i.e. R²) and r is an integer from 0 to 4, limitedby the number of available positions on each U group. As U-29, U-30,U-36, U-37, U-38, U-39, U-40, U-41, U-42 and U-43 have only oneavailable position, for these U groups r is limited to the integers 0 or1, and r being 0 means that the U group is unsubstituted and a hydrogenis present at the position indicated by (R^(v))_(r).

Exhibit 2

Note that when Q¹ is a 5- or 6-membered saturated or non-aromaticunsaturated heterocyclic ring optionally substituted with one or moresubstituents selected from the group of substituents as defined in theSummary of Invention for Q¹, one or two carbon ring members of theheterocycle can optionally be in the oxidized form of a carbonyl moiety.

Examples of a 5- or 6-membered saturated or non-aromatic unsaturatedheterocyclic ring include the rings G-1 through G-35 as illustrated inExhibit 3. Note that when the attachment point on the G group isillustrated as floating, the G group can be attached to the remainder ofFormula 1 through any available carbon or nitrogen of the G group byreplacement of a hydrogen atom. The optional substituents correspondingto R^(v) can be attached to any available carbon or nitrogen byreplacing a hydrogen atom. For these G rings, r is typically an integerfrom 0 to 4, limited by the number of available positions on each Ggroup.

Note that when Q¹ comprises a ring selected from G-28 through G-35, G²is selected from O, S or N. Note that when G² is N, the nitrogen atomcan complete its valence by substitution with either H or thesubstituents corresponding to R^(v) as defined in the Summary ofInvention for Q¹ (i.e. R²).

Exhibit 3

As noted above, Q¹ can be (among others) an 8-, 9- or 10-membered fusedbicyclic ring system optionally substituted with one or moresubstituents selected from a group of substituents as defined in theSummary of Invention (i.e. R²). Examples of 8-, 9- or 10-membered fusedbicyclic ring system optionally substituted with from one or moresubstituents include the rings U-81 through U-123 illustrated in Exhibit4 wherein R^(v) is any substituent as defined in the Summary of theInvention for Q¹ (i.e. R²), and r is typically an integer from 0 to 4.

Exhibit 4

Although R^(v) groups are shown in the structures U-1 through U-123, itis noted that they do not need to be present since they are optionalsubstituents. Note that when R^(v) is H when attached to an atom, thisis the same as if said atom is unsubstituted. The nitrogen atoms thatrequire substitution to fill their valence are substituted with H orR^(v). Note that when the attachment point between (R^(v))_(r) and the Ugroup is illustrated as floating, (R^(v))_(r) can be attached to anyavailable carbon atom or nitrogen atom of the U group. Note that whenthe attachment point on the U group is illustrated as floating, the Ugroup can be attached to the remainder of Formula 1 through anyavailable carbon or nitrogen of the U group by replacement of a hydrogenatom. Note that some U groups can only be substituted with less than 4R^(v) groups (e.g., U-2 through U-5, U-7 through U-48, and U-52 throughU-61).

A wide variety of synthetic methods are known in the art to enablepreparation of aromatic and nonaromatic heterocyclic rings and ringsystems; for extensive reviews see the eight volume set of ComprehensiveHeterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief,Pergamon Press, Oxford, 1984 and the twelve volume set of ComprehensiveHeterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V.Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds of this invention can exist as one or more stereoisomers. Thevarious stereoisomers include enantiomers, diastereomers, atropisomersand geometric isomers. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. The compounds of the invention may be present as amixture of stereoisomers, individual stereoisomers or as an opticallyactive form. For example, two possible enantiomers of Formula 1 aredepicted as Formula 1′ and Formula 1″ involving the isoxazoline chiralcenter identified with an asterisk (*). Analogously, other chiralcenters are possible at, for example, R⁵.

Molecular depictions drawn herein follow standard conventions fordepicting stereochemistry. To indicate stereoconfiguration, bonds risingfrom the plane of the drawing and towards the viewer are denoted bysolid wedges wherein the broad end of the wedge is attached to the atomrising from the plane of the drawing towards the viewer. Bonds goingbelow the plane of the drawing and away from the viewer are denoted bydashed wedges wherein the narrow end of the wedge is attached to theatom further away from the viewer. Constant width lines indicate bondswith a direction opposite or neutral relative to bonds shown with solidor dashed wedges; constant width lines also depict bonds in molecules orparts of molecules in which no particular stereoconfiguration isintended to be specified.

The more biologically active enantiomer is believed to be Formula 1′.Formula 1′ often has the (5) configuration at the chiral carbon andFormula 1″ often has the (R) configuration at the chiral carbon (e.g.,when Q is phenyl and R¹ is trifluoromethyl).

This invention comprises racemic mixtures, for example, equal amounts ofthe enantiomers of Formulae 1′ and 1″. In addition, this inventionincludes compounds that are enriched compared to the racemic mixture inan enantiomer of Formula 1. Also included are the essentially pureenantiomers of compounds of Formula 1, for example, Formula 1′ andFormula 1″.

When enantiomerically enriched, one enantiomer is present in greateramounts than the other, and the extent of enrichment can be defined byan expression of enantiomeric excess (“ee”), which is defined as(2×−1)·100%, where x is the mole fraction of the dominant enantiomer inthe mixture (e.g., an ee of 20% corresponds to a 60:40 ratio ofenantiomers).

Preferably the compositions of this invention have at least a 50%enantiomeric excess; more preferably at least a 75% enantiomeric excess;still more preferably at least a 90% enantiomeric excess; and the mostpreferably at least a 94% enantiomeric excess of the more active isomer.Of particular note are enantiomerically pure embodiments of the moreactive isomer.

Compounds of Formula 1 can comprise additional chiral centers. Forexample, substituents and other molecular constituents such as R⁵ maythemselves contain chiral centers. This invention comprises racemicmixtures as well as enriched and essentially pure stereo configurationsat these additional chiral centers.

Compounds of this invention can exist as one or more conformationalisomers due to restricted rotation about the amide bond linking Q-A toZ¹ and Q-B to Z². This invention comprises mixtures of conformationalisomers. In addition, this invention includes compounds that areenriched in one conformer relative to others.

Compounds of this invention may exist as one or more crystallinepolymorphs. This invention comprises both individual polymorphs andmixtures of polymorphs, including mixtures enriched in one polymorphrelative to others.

One skilled in the art will appreciate that not all nitrogen-containingheterocycles can form N-oxides since the nitrogen requires an availablelone pair for oxidation to the oxide; one skilled in the art willrecognize those nitrogen containing heterocycles which can formN-oxides. One skilled in the art will also recognize that tertiaryamines can form N-oxides. Synthetic methods for the preparation ofN-oxides of heterocycles and tertiary amines are very well known by oneskilled in the art including the oxidation of heterocycles and tertiaryamines with peroxy acids such as peracetic and m-chloroperbenzoic acid(MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butylhydroperoxide, sodium perborate, and dioxiranes such asdimethyldioxirane. These methods for the preparation of N-oxides havebeen extensively described and reviewed in the literature, see forexample: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik inComprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boultonand A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keenein Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R.Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advancesin Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J.Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G.Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A.R. Katritzky and A. J. Boulton, Eds., Academic Press.

One skilled in the art recognizes that because in the environment andunder physiological conditions salts of chemical compounds are inequilibrium with their corresponding nonsalt forms, salts share thebiological utility of the nonsalt forms. Thus a wide variety of salts ofthe compounds of Formula 1 are useful for control of invertebrate pests(i.e. are agriculturally suitable). The salts of the compounds ofFormula 1 include acid-addition salts with inorganic or organic acidssuch as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic,butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic,tartaric, 4-toluenesulfonic or valeric acids. When a compound of Formula1 contains an acidic moiety such as a carboxylic acid or phenol, saltsalso include those formed with organic or inorganic bases such aspyridine, triethylamine or ammonia, or amides, hydrides, hydroxides orcarbonates of sodium, potassium, lithium, calcium, magnesium or barium.As is well known in the art, when a compound containing a carboxylicacid group (i.e. CO₂H) is contacted with a base, the carboxylic acidgroup is converted to its salt derivative, also known as a carboxylatesalt. For example, when a carboxylic acid group is reacted with sodiumhydroxide, a sodium salt derivative is formed (i.e. CO₂e^(⊖)Na^(⊕)).Accordingly, the present invention comprises compounds selected fromFormula 1, N-oxides and agriculturally suitable salts thereof.

Embodiments of the present invention as described in the Summary of theInvention include (where Formula 1 as used in the following Embodimentsincludes N-oxides and salts thereof):

-   -   Embodiment 1. A compound of Formula 1 wherein Q is Q-A.    -   Embodiment 2. A compound of Embodiment 1 wherein Z¹ is Z¹-1.    -   Embodiment 3. A compound of Embodiment 1 wherein Z¹ is Z¹-2.    -   Embodiment 4. A compound of Embodiment 1 wherein Z¹ is Z¹-3.    -   Embodiment 5. A compound of Embodiment 1 wherein Y¹—Y²—Y³ is        —CH═CH—S—, —CH═CH—O—, —S—CH═CH— or —O—CH═CH—.    -   Embodiment 6. A compound of Formula 1 wherein Q is Q-B.    -   Embodiment 7. A compound of Embodiment 6 wherein Z² is Z²-1.    -   Embodiment 8. A compound of Embodiment 6 wherein Z² is Z²-2.    -   Embodiment 9. A compound of Formula 1 wherein when Q is Q-B, Z²        is Z²-2, R¹⁰ is C₁ alkyl substituted with one R³⁵, and R³⁵ is        CO₂H or a sodium salt derivative thereof, then R⁹ is other than        H.    -   Embodiment 10. A compound of Formula 1 wherein when Q is Q-B, Z²        is Z²-2, R¹⁰ is C₁ alkyl substituted with one R³⁵, and R³⁵ is        CO₂H or a salt derivative thereof, then R⁹ is other than H.    -   Embodiment 11. A compound of Embodiment 6 wherein Z² is Z²-3.    -   Embodiment 12. A compound of Embodiment 11 wherein        -   R¹¹ is H;        -   R¹² is H or C₁-C₃ alkyl;        -   R¹³ is H or C₁-C₃ alkyl;        -   R¹⁴ is C₁-C₆ alkyl, C₃-C₆ cycloalkyl or C₄-C₇            alkylcycloalkyl optionally substituted with one or more            substituents independently selected from R³⁵;        -   R³⁵ is H, halogen, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆            alkylthio, C₁-C₆ haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆            haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆            haloalkylsulfonyl, CN or NO₂; and        -   Y⁴ is CH.    -   Embodiment 12a. A compound of Embodiment 12 wherein        -   R¹² is H;        -   R¹³ is H or CH₃;        -   R¹⁴ is cyclopropyl or methylcyclopropyl optionally            substituted with one or more substituents independently            selected from R³⁵;        -   R¹⁵ is H; and        -   R³⁵ is H or halogen.    -   Embodiment 13. A compound of Embodiment 6 wherein Z² is Z²-4.    -   Embodiment 14. A compound of Embodiment 6 wherein Z² is Z²-5.    -   Embodiment 15. A compound of Formula 1 wherein R¹ is C₁-C₃        haloalkyl.    -   Embodiment 16. A compound of Embodiment 15 wherein R¹ is CF₃.    -   Embodiment 17. A compound of Formula 1 wherein A is a phenyl        ring substituted with 1 to 3 substituents independently selected        from the group consisting of halogen, C₁-C₃ alkyl, C₁-C₃        haloalkyl, C₁-C₃ haloalkoxy and CN.    -   Embodiment 17a. A compound of Embodiment 17 wherein A is a        phenyl ring substituted with 2 substituents independently        selected from the group consisting of halogen, C₁-C₂ haloalkyl        and C₁-C₂ haloalkoxy.    -   Embodiment 18. A compound of Embodiment 17 wherein A is a phenyl        ring substituted with 1 to 3 substituents independently selected        from the group consisting of halogen, CH₃, CF₃, OCF₃, OCF₂H and        CN.    -   Embodiment 19. A compound of Formula 1 wherein A is a pyridyl        ring substituted with 1 to 3 substituents independently selected        from the group consisting of halogen, C₁-C₃ alkyl, C₁-C₃        haloalkyl, C₁-C₃ haloalkoxy and CN.    -   Embodiment 20. A compound of Embodiment 19 wherein A is a        pyridyl ring substituted with 1 to 3 substituents independently        selected from the group consisting of halogen, CH₃, CF₃, OCF₃,        OCF₂H and CN.    -   Embodiment 21. A compound of Formula 1 wherein W¹, W², W³, W⁴,        W⁵ and W⁶ are O.

Embodiment 22. A compound of Embodiment 2 wherein

-   -   -   R⁵ is H; or C₁-C₆ alkyl substituted with one or more            substituents independently selected from R²²; and        -   R⁶ is C₁-C₆ alkyl or C₃-C₇ alkylcycloalkyl, each optionally            substituted with one or more substituents independently            selected from R³³.

    -   Embodiment 23. A compound of Embodiment 22 wherein R²² and R³³        are independently selected from the group consisting of halogen,        C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆        alkylsulfinyl, C₁-C₆ alkylsulfonyl, CN, NO₂, CO₂R³⁷,        C(═O)NR³⁷R³⁸ and Q¹.

    -   Embodiment 24. A compound of Embodiment 3 wherein        -   R¹⁶ and R¹⁷ are independently C₁-C₃ alkyl optionally            substituted with one or more substituents independently            selected from R³⁵; and        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN.

    -   Embodiment 25. A compound of Embodiment 4 wherein        -   L¹ is C₂-C₆ alkylene optionally substituted with halogen;        -   R¹⁹ is C₁-C₃ alkyl optionally substituted with one or more            substituents independently selected from R³⁵;        -   R²⁰ is H, CN, NO₂ or CO₂R²⁴;        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN; and        -   q is 1.

    -   Embodiment 26. A compound of Embodiment 13 wherein        -   R¹⁶ and R¹⁷ are independently C₁-C₃ alkyl optionally            substituted with one or more substituents independently            selected from R³⁵; and        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN.

    -   Embodiment 27. A compound of Embodiment 14 wherein        -   L¹ is C₂-C₆ alkylene optionally substituted with one or more            halogen;        -   R¹⁹ is C₁-C₃ alkyl optionally substituted with one or more            substituents independently selected from R³⁵;        -   R²⁰ is H, CN, NO₂ or CO₂R²⁴;        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN; and        -   q is 1.

Embodiments of this invention, including Embodiments 1-27 above as wellas any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1 but also to the starting compoundsand intermediate compounds useful for preparing the compounds ofFormula 1. In addition, embodiments of this invention, includingEmbodiments 1-27 above as well as any other embodiments describedherein, and any combination thereof, pertain to the compositions andmethods of the present invention.

Combinations of Embodiments 1-27 are illustrated by:

-   -   Embodiment A. A compound of Formula 1 wherein        -   Q is Q-A;        -   Z¹ is Z¹-1;        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN; and        -   R¹ is C₁-C₃ haloalkyl.    -   Embodiment B. A compound of Embodiment A wherein        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment C. A compound of Formula 1 wherein        -   Q is Q-A;        -   Z¹ is Z¹-1;        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN; and        -   R¹ is C₁-C₃ haloalkyl.    -   Embodiment D. A compound of Embodiment C wherein        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment E. A compound of Embodiment A wherein        -   R⁵ is H; or C₁-C₆ alkyl substituted with one or more            substituents independently selected from R²²; and        -   R⁶ is C₁-C₆ alkyl or C₃-C₇ alkylcycloalkyl, each optionally            substituted with one or more substituents independently            selected from R³³.    -   Embodiment F. A compound of Embodiment B wherein        -   R⁵ is H; or C₁-C₆ alkyl substituted with one or more            substituents independently selected from R²²; and        -   R⁶ is C₁-C₆ alkyl or C₃-C₇ alkylcycloalkyl, each optionally            substituted with one or more substituents independently            selected from R³³.    -   Embodiment G. A compound of Embodiment C wherein        -   R⁵ is H; or C₁-C₆ alkyl substituted with one or more            substituents independently selected from R²²; and        -   R⁶ is C₁-C₆ alkyl or C₃-C₇ alkylcycloalkyl, each optionally            substituted with one or more substituents independently            selected from R³³.    -   Embodiment H. A compound of Embodiment D wherein        -   R⁵ is H; or C₁-C₆ alkyl substituted with one or more            substituents independently selected from R²²; and        -   R⁶ is C₁-C₆ alkyl or C₃-C₇ alkylcycloalkyl, each optionally            substituted with one or more substituents independently            selected from R³³.    -   Embodiment I. A compound of Embodiment E wherein        -   R²² and R³³ are independently selected from the group            consisting of halogen, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆            alkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, CN,            NO₂, CO₂R³⁷, C(═O)NR³⁷R³⁸ and Q¹.    -   Embodiment J. A compound of Embodiment F wherein        -   R²² and R³³ are independently selected from the group            consisting of halogen, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆            alkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, CN,            NO₂, CO₂R³⁷, C(═O)NR³⁷R³⁸ and Q¹.    -   Embodiment K. A compound of Embodiment G wherein        -   R²² and R³³ are independently selected from the group            consisting of halogen, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆            alkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, CN,            NO₂, CO₂R³⁷, C(═O)NR³⁷R³⁸ and Q¹.    -   Embodiment L. A compound of Embodiment H wherein        -   R²² and R³³ are independently selected from the group            consisting of halogen, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆            alkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, CN,            NO₂, CO₂R³⁷, C(═O)NR³⁷R³⁸ and Q¹.    -   Embodiment M. A compound of Formula 1 wherein        -   Q is Q-A;        -   Z¹ is Z¹-2;        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN; and        -   R¹ is C₁-C₃ haloalkyl.    -   Embodiment N. A compound of Embodiment M wherein        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment O. A compound of Formula 1 wherein        -   Q is Q-A;        -   Z¹ is Z¹-2;        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN; and        -   R¹ is C₁-C₃ haloalkyl.    -   Embodiment P. A compound of Embodiment O wherein        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment Q. A compound of Embodiment M wherein        -   R¹⁶ and R¹⁷ are independently C₁-C₃ alkyl optionally            substituted with one or more substituents independently            selected from R³⁵; and        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN.    -   Embodiment R. A compound of Embodiment N wherein        -   R¹⁶ and R¹⁷ are independently C₁-C₃ alkyl optionally            substituted with one or more substituents independently            selected from R³⁵; and        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN.    -   Embodiment S. A compound of Embodiment O wherein        -   R¹⁶ and R¹⁷ are independently C₁-C₃ alkyl optionally            substituted with one or more substituents independently            selected from R³⁵; and        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN.    -   Embodiment T. A compound of Embodiment P wherein        -   R¹⁶ and R¹⁷ are independently C₁-C₃ alkyl optionally            substituted with one or more substituents independently            selected from R³⁵; and        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN.    -   Embodiment U. A compound of Formula 1 wherein        -   Q is Q-A;        -   Z¹ is Z¹-3;        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN;        -   R¹ is C₁-C₃ haloalkyl;        -   L¹ is C₂-C₆ alkylene optionally substituted with halogen;        -   R¹⁹ is C₁-C₃ alkyl optionally substituted with one or more            substituents independently selected from R³⁵;        -   R²⁰ is H, CN, NO₂ or CO₂R²⁴;        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN; and        -   q is 1    -   Embodiment V. A compound of Embodiment U wherein        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment W. A compound of Formula 1 wherein        -   Q is Q-A;        -   Z¹ is Z¹-3;        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN;        -   R¹ is C₁-C₃ haloalkyl;        -   L¹ is C₂-C₆ alkylene optionally substituted with halogen;        -   R¹⁹ is C₁-C₃ alkyl optionally substituted with one or more            substituents independently selected from R³⁵;        -   R²⁰ is H, CN, NO₂ or CO₂R²⁴;        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN; and        -   q is 1.    -   Embodiment X. A compound of Embodiment W wherein        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment Y. A compound of Formula 1 wherein        -   Q is Q-B;        -   Z² is Z²-3;        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN;        -   R¹ is C₁-C₃ haloalkyl;        -   R¹¹ is H;        -   R¹² is H or C₁-C₃ alkyl;        -   R¹³ is H or C₁-C₃ alkyl;        -   R¹⁴ is C₁-C₆ alkyl, C₃-C₆ cycloalkyl or C₄-C₇            alkylcycloalkyl optionally substituted with one or more            substituents independently selected from R³⁵; and        -   R³⁵ is H, halogen, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆            alkylthio, C₁-C₆ haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆            haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆            haloalkylsulfonyl, CN or NO₂; and        -   Y⁴ is CH.    -   Embodiment Z. A compound of Embodiment Y wherein        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment AA. A compound of Formula 1 wherein        -   Q is Q-B;        -   Z² is Z²-3;        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN;        -   R¹ is C₁-C₃ haloalkyl;        -   R¹¹ is H;        -   R¹² is H or C₁-C₃ alkyl;        -   R¹³ is H or C₁-C₃ alkyl;        -   R¹⁴ is C₁-C₆ alkyl, C₃-C₆ cycloalkyl or C₄-C₇            alkylcycloalkyl optionally substituted with one or more            substituents independently selected from R³⁵; and        -   R³⁵ is H, halogen, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆            alkylthio, C₁-C₆ haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆            haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆            haloalkylsulfonyl, CN or NO₂.    -   Embodiment AB. A compound of Embodiment AA wherein        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment AC. A compound of Formula 1 wherein        -   Q is Q-B;        -   Z² is Z²-4;        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN;        -   R¹ is C₁-C₃ haloalkyl;        -   R¹⁶ and R¹⁷ are independently C₁-C₃ alkyl optionally            substituted with one or more substituents independently            selected from R³⁵; and        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN.    -   Embodiment AD. A compound of Embodiment AC wherein        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment AE. A compound of Formula 1 wherein        -   Q is Q-B;        -   Z² is Z²-4;        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN;        -   R¹ is C₁-C₃ haloalkyl;        -   R¹⁶ and R¹⁷ are independently C₁-C₃ alkyl optionally            substituted with one or more substituents independently            selected from R³⁵; and        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN.    -   Embodiment AF. A compound of Embodiment AE wherein        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment AG. A compound of Formula 1 wherein        -   Q is Q-B;        -   Z² is Z⁵-5;        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN;        -   R¹ is C₁-C₃ haloalkyl;        -   L¹ is C₂-C₆ alkylene optionally substituted with halogen;        -   R¹⁹ is C₁-C₃ alkyl optionally substituted with one or more            substituents independently selected from R³⁵;        -   R²⁰ is H, CN, NO₂ or CO₂R²⁴;        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN; and        -   q is 1.    -   Embodiment AH. A compound of Embodiment AG wherein        -   A is a phenyl ring substituted with 1 to 3 substituents            independently selected from the group consisting of halogen,            CH₃, CF₃, OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment AI. A compound of Formula 1 wherein        -   Q is Q-B;        -   Z² is Z²-5;        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group halogen, C₁-C₃ alkyl,            C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN;        -   R¹ is C₁-C₃ haloalkyl;        -   L¹ is C₂-C₆ alkylene optionally substituted with halogen;        -   R¹⁹ is C₁-C₃ alkyl optionally substituted with one or more            substituents independently selected from R³⁵;        -   R²⁰ is H, CN, NO₂ or CO₂R²⁴;        -   R³⁵ is halogen, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN; and        -   q is 1.    -   Embodiment AJ. A compound of Embodiment AI wherein        -   A is a pyridyl ring substituted with 1 to 3 substituents            independently selected from the group halogen, CH₃, CF₃,            OCF₃, OCF₂H and CN; and        -   R¹ is CF₃.    -   Embodiment AK. A compound of Embodiment Y wherein        -   A is a phenyl ring substituted with 2 substituents            independently selected from the group consisting of halogen,            C₁-C₂ haloalkyl and C₁-C₂ haloalkoxy;        -   R¹ is CF₃;        -   R¹² is H;        -   R¹³ is H or CH₃;        -   R¹⁴ is cyclopropyl or methylcyclopropyl optionally            substituted with one or more substituents independently            selected from R³⁵;        -   R¹⁵ is H;        -   R³⁵ is H or halogen.

Specific embodiments include compounds of Formula 1 selected from thegroup consisting of:

-   N-[2-[(cyclopropylmethyl)amino]-2-oxoethyl]-4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide,-   4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-[(2-methoxyethyl)amino]-2-oxoethyl]-1-naphthalenecarboxamide,-   4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-(S-methylsulfonimidoyl)ethyl]-1-naphthalenecarboxamide,-   N-[2-[(cyclopropyl-1-methylethyl)amino]-2-oxoethyl]-4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide,-   4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-oxo-2-[(2-pyridinylmethyl)amino]ethyl]-1-naphthalenecarboxamide,-   N-[2-(cyclopropylamino]-2-oxoethyl]-4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide,-   1,1-dimethylethyl    N-[2-[[[4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]carbonyl]amino]ethyl]carbamate,-   1,1-dimethylethyl    N-[3-[[[4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]carbonyl]amino]propyl]-N-methylcarbamate,-   N-[3-(acetylmethylamino)propyl]-4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide,-   4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-[[2-(methylthio)ethyl]amino]-2-oxoethyl]-1-naphthalenecarboxamide,-   4-[4,5-dihydro-5-(3,4,5-trichlorophenyl)-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-[[2-(methylthio)ethyl]amino]-2-oxoethyl]-1-naphthalenecarboxamide,-   N-[2-(cyclopentylamino)-2-oxoethyl]-4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide,-   4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-oxo-2-(1-piperidinyl)ethyl]-1-naphthalenecarboxamide,-   4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-(3,3-difluoro-1-pyrrolidinyl)-2-oxoethyl]-1-naphthalenecarboxamide,    and-   4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-[S-methyl-N-(2,2,2-trifluoroacetyl)sulfonimidoyl]ethyl]-1-naphthalenecarboxamide.

Further specific embodiments include compounds of Formula 1 selectedfrom Table A. The following abbreviations are used in Table A: c-Pr iscyclopropyl and entry a) is

TABLE A

R^(a) R^(b) R^(c) R^(d) Cl Cl H c-Pr Cl Cl H CH₂-c-Pr Cl Cl H a) Cl ClCH₃ c-Pr Cl Cl CH₃ CH₂-c-Pr Cl Cl CH₃ a) Cl CF₃ H c-Pr Cl CF₃ H CH₂-c-PrCl CF₃ H a) Cl CF₃ CH₃ c-Pr Cl CF₃ CH₃ CH₂-c-Pr Cl CF₃ CH₃ a) Cl OCH₂CF₃H c-Pr Cl OCH₂CF₃ H CH₂-c-Pr Cl OCH₂CF₃ H a) Cl OCH₂CF₃ CH₃ c-Pr ClOCH₂CF₃ CH₃ CH₂-c-Pr Cl OCH₂CF₃ CH₃ a) Br CF₃ H c-Pr Br CF₃ H CH₂-c-PrBr CF₃ H a) Br CF₃ CH₃ c-Pr Br CF₃ CH₃ CH₂-c-Pr Br CF₃ CH₃ a) CF₃ CF₃ Hc-Pr CF₃ CF₃ H CH₂-c-Pr CF₃ CF₃ H a) CF₃ CF₃ CH₃ c-Pr CF₃ CF₃ CH₃CH₂-c-Pr CF₃ CF₃ CH₃ a)

Further noteworthy as embodiments of the present invention arecompositions for controlling an invertebrate pest comprising a compoundof any of the preceding Embodiments (i.e. in a biologically effectiveamount), as well as any other embodiments described herein, and anycombinations thereof, and at least one additional component selectedfrom the group consisting of a surfactant, a solid diluent and a liquiddiluent, said compositions optionally further comprising at least oneadditional biologically active compound or agent.

Further Embodiments of the present invention include:

-   -   Embodiment A1. A composition for protecting an animal from an        invertebrate parasitic pest comprising a compound of Formula 1        or any one of Embodiments 1-27 or A-AK and at least one        veterinarily acceptable carrier, said composition optionally        further comprising at least one additional parasiticidally        active compound.    -   Embodiment A2. The composition of Embodiment A1 wherein at least        one additional parasiticidally active compound is an        anthelmintic.    -   Embodiment A3. The composition of Embodiment A1 wherein at least        one additional parasiticidally active compound is selected from        the group consisting of macrocyclic lactones, benzimidazoles,        salicylamides, substituted phenols, pyrimidines, cyclic        depsipeptides, piperazine salts, nitroscanate, praziquantel and        imidazothiazoles.    -   Embodiment A4. The composition of Embodiment A3 wherein at least        one additional parasiticidally active compound is selected from        the group consisting of avermectins, milbemycins and spinosyns.    -   Embodiment A5. The composition of Embodiment A1 wherein at least        one additional parasiticidally active compound is selected from        the group consisting of abamectin, doramectin, emamectin,        eprinomectin, ivermectin, selamectin, milbemycin, moxidectin and        pyrantel.    -   Embodiment A6. The composition of Embodiment A1 in a form for        oral administration.    -   Embodiment A7. The composition of Embodiment A1 in a form for        topical administration.    -   Embodiment A8. The composition of Embodiment A1 in a form for        parenteral administration.

Embodiments of the invention further include methods for controlling aninvertebrate pest comprising contacting the invertebrate pest or itsenvironment with a biologically effective amount of a compound of any ofthe preceding Embodiments (e.g., as a composition described herein). Ofparticular note is a method for protecting an animal comprisingadministering to the animal a parasiticidally effective amount of acompound of any of the preceding Embodiments (e.g., as a compositiondescribed herein).

Further Embodiments of the present invention include:

-   -   Embodiment B1. The method for protecting an animal from an        invertebrate parasitic pest comprising administering to the        animal a parasiticidally effective amount of a compound of        Formula 1 as described in the Summary of the Invention or any        one of Embodiments 1-27 or A-AK.    -   Embodiment B3. The method of Embodiment B1 wherein the        parasiticidally effective amount of the compound of Formula 1 is        administered orally.    -   Embodiment B4. The method of Embodiment B1 wherein the        parasiticidally effective amount of the compound of Formula 1 is        administered parenterally.    -   Embodiment B5. The method of Embodiment B1 wherein the        parasiticidally effective amount of the compound of Formula 1 is        administered by injection.    -   Embodiment B6. The method of Embodiment B1 wherein the        parasiticidally effective amount of the compound of Formula 1 is        administered topically.    -   Embodiment B7. The method of Embodiment B1 wherein the animal to        be protected is a vertebrate.    -   Embodiment B8. The method of Embodiment B7 wherein the animal to        be protected is a mammal, avian or fish.    -   Embodiment B9. The method of Embodiment B8 wherein the animal to        be protected is a human.    -   Embodiment B10. The method of Embodiment B8 wherein the animal        to be protected is livestock.    -   Embodiment B11. The method of Embodiment B8 wherein the animal        to be protected is a canine.    -   Embodiment B11a. The method of Embodiment B8 wherein the animal        to be protected is a dog.    -   Embodiment B12. The method of Embodiment B8 wherein the animal        to be protected is a feline.    -   Embodiment B12a. The method of Embodiment B8 wherein the animal        to be protected is a cat.    -   Embodiment B13. The method of Embodiment B1 wherein the        invertebrate parasitic pest is an ectoparasite.    -   Embodiment B14. The method of Embodiment B1 wherein the        invertebrate parasitic pest is an endoparasite or helminth.    -   Embodiment B15. The method of Embodiment B1 wherein the        invertebrate parasitic pest is an arthropod.    -   Embodiment B16. The method of Embodiment B1 wherein the        invertebrate parasitic pest is a fly, mosquito, mite, tick,        louse, flea, maggot, bed bug or kissing bug.    -   Embodiment B17. The method of Embodiment B16 wherein the        invertebrate parasitic pest is a mosquito.    -   Embodiment B18. The method of Embodiment B16 wherein the        invertebrate parasitic pest is a tick or mite.    -   Embodiment B19. The method of Embodiment B16 wherein the        invertebrate parasitic pest is a louse.    -   Embodiment B20. The method of Embodiment B16 wherein the        invertebrate parasitic pest is a flea.    -   Embodiment B21. The method of Embodiment B16 wherein the        invertebrate parasitic pest is a bed bug or kissing bug.    -   Embodiment B22. The method of Embodiment B16 wherein the animal        is a cat or dog and the invertebrate parasitic pest is a flea,        tick or mite.    -   Embodiment B23. The method of Embodiment B1 wherein the        parasiticidally effective amount of a compound of Formula 1 is        administered monthly or at a longer interval.    -   Embodiment B24. The method of Embodiment B23 wherein the        parasiticidally effective amount of a compound of Formula 1 is        administered once a month.    -   Embodiment B25. The method of Embodiment B23 wherein the        parasiticidally effective amount of a compound of Formula 1 is        administered once every six months.

The compounds of Formula 1 or any of Embodiments 1-27 or EmbodimentsA-AK can be used for the protection of an animal from an invertebrateparasitic pest by oral, topical or parenteral administration of thecompound.

Therefore, the invention is understood to include the compounds ofFormula 1 or any of Embodiments 1-27 or Embodiments A-AK (andcompositions containing them) for use as an animal medicament, or moreparticularly a parasiticidal animal medicament. The animals to beprotected are as defined in any of Embodiments B7-B12a. The invertebrateparasitic pests are as defined in any of Embodiments B13-B21. Themedicament may be in oral, topical or parenteral dosage forms.

The invention is also understood to include the use of compounds ofFormula 1 or any of Embodiments 1-27 or Embodiments A-AK in themanufacture of medicaments for the protection of an animal from a aninvertebrate parasitic pest. The animals to be protected are as definedin any of Embodiments B7-B12a. The invertebrate parasitic pests are asdefined in any of Embodiments B13-B21. The medicament may be in oral,topical or parenteral dosage forms.

The invention is also understood to include compounds of Formula 1 orany of Embodiments 1-27 or Embodiments A-AK for use in the manufactureof medicaments for the protection of an animal from an invertebrateparasitic pest. The animals to be protected are as defined in any ofEmbodiments B7-B12a. The invertebrate parasitic pests are as defined inany of Embodiments B13-B21. The medicament may be in oral, topical orparenteral dosage forms.

The invention is also understood to include compounds of Formula 1 orany of Embodiments 1-27 or Embodiments A-AK packaged and presented forthe protection of an animal from an invertebrate parasitic pest. Theanimals to be protected are as defined in any of Embodiments B7-B12a.The invertebrate parasitic pests are as defined in any of EmbodimentsB13-B21. The compounds of the invention may be packaged and presented asoral, topical or parenteral dosage forms.

The invention is also understood to include a process for manufacturinga composition for protecting an animal from an invertebrate parasiticpest characterized in that a compound of claim 1 is admixed with atleast one pharmaceutically or veterinarily acceptable carrier. Theanimals to be protected are as defined in any of Embodiments B7-B12a.The invertebrate parasitic pests are as defined in any of EmbodimentsB13-B21. The compositions of the invention may be packaged and presentedas oral, topical or parenteral dosage forms.

Of note is that compounds of this invention are characterized byfavorable metabolic and/or soil residual patterns and exhibit activitycontrolling a spectrum of agronomic and nonagronomic invertebrate pests.

Of particular note, for reasons of invertebrate pest control spectrumand economic importance, protection of agronomic crops from damage orinjury caused by invertebrate pests by controlling invertebrate pestsare embodiments of the invention. Compounds of this invention because oftheir favorable translocation properties or systemicity in plants alsoprotect foliar or other plant parts which are not directly contactedwith a compound of Formula 1 or a composition comprising the compound.

Also noteworthy as embodiments of the present invention are compositionscomprising a compound of any of the preceding Embodiments, as well asany other embodiments described herein, and any combinations thereof,and at least one additional component selected from the group consistingof a surfactant, a solid diluent and a liquid diluent, said compositionsoptionally further comprising at least one additional biologicallyactive compound or agent.

Further noteworthy as embodiments of the present invention arecompositions for controlling an invertebrate pest comprising abiologically effective amount of a compound of any of the precedingEmbodiments, as well as any other embodiments described herein, and anycombinations thereof, and at least one additional component selectedfrom the group consisting of a surfactant, a solid diluent and a liquiddiluent, said compositions optionally further comprising a biologicallyeffective amount of at least one additional biologically active compoundor agent. Embodiments of the invention further include methods forcontrolling an invertebrate pest comprising contacting the invertebratepest or its environment with a biologically effective amount of acompound of any of the preceding Embodiments (e.g., as a compositiondescribed herein).

Embodiments of the invention also include a composition comprising acompound of any of the preceding Embodiments, in the form of a soildrench liquid formulation. Embodiments of the invention further includemethods for controlling an invertebrate pest comprising contacting thesoil with a liquid composition as a soil drench comprising abiologically effective amount of a compound of any of the precedingEmbodiments.

Embodiments of the invention also include a spray composition forcontrolling an invertebrate pest comprising a biologically effectiveamount of a compound of any of the preceding Embodiments and apropellant. Embodiments of the invention further include a baitcomposition for controlling an invertebrate pest comprising abiologically effective amount of a compound of any of the precedingEmbodiments, one or more food materials, optionally an attractant, andoptionally a humectant. Embodiments of the invention also include adevice for controlling an invertebrate pest comprising said baitcomposition and a housing adapted to receive said bait composition,wherein the housing has at least one opening sized to permit theinvertebrate pest to pass through the opening so the invertebrate pestcan gain access to said bait composition from a location outside thehousing, and wherein the housing is further adapted to be placed in ornear a locus of potential or known activity for the invertebrate pest.

One or more of the following methods and variations as described inSchemes 1-30 can be used to prepare the compounds of Formula 1. Thedefinitions of R¹, R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, A, L¹, W¹, W⁴, W⁵, Y¹, Y², Y³, Y⁴, m and nin the compounds of Formulae 1-33 below are as defined above in theSummary of the Invention unless otherwise noted. Formulae 1a-1j arevarious subsets of Formula 1, and all substituents for Formulae 1a-1jare as defined above for Formula 1.

As shown in Scheme 1, compounds of Formula 1b (Formula 1 wherein Q isQ-A, Z¹ is Z¹-1 and W¹ is S) can be prepared by treatment ofcorresponding amide compounds of Formula 1a (compounds of Formula 1wherein Q is Q-A, Z¹ is Z¹-1 and W¹ is O) with a thio transfer reagent,such as P₂S₅ (see for example, E. Klingsberg et al., J. Am. Chem. Soc.1951, 72, 4988; E. C. Taylor Jr. et al., J. Am. Chem. Soc. 1953, 75,1904; R. Crossley et al., J. Chem. Soc. Perkin Trans. 1 1976, 977) orLawesson's reagent(2,5-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide;see, for example, S. Prabhakar et al. Synthesis, 1984, 829). The methodof Scheme 1 can be conducted over a wide range of temperatures,including from about 50 to about 150° C. Of note are temperatures fromabout 70 to about 120° C., which typically provide fast reaction ratesand high product yields.

As shown in Scheme 2, compounds of Formula 1a can be prepared bycoupling carboxylic acids of Formula 2 with appropriately substitutedamino compounds of Formula 3. This reaction is generally carried out inthe presence of a dehydrating coupling reagent, such as dicyclohexylcarbodiimide (DCC), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide,1-propanephosphonic acid cyclic anhydride or carbonyl diimidazole, inthe presence of a base such as triethylamine, pyridine,4-(dimethylamino)pyridine or N,N-diisopropylethylamine in an anhydrousaprotic solvent such as dichloromethane or tetrahydrofuran at atemperature typically between room temperature and 70° C.

As shown in Scheme 3, compounds of Formula 1a can also be prepared byaminocarbonylation of aryl bromides of Formula 4 with appropriatelysubstituted amino compounds of Formula 3. This reaction is typicallycarried out with an aryl bromide of Formula 4 in the presence of apalladium catalyst under CO atmosphere. The palladium catalysts used forthe present method typically comprises palladium in a formal oxidationstate of either 0 (i.e. Pd(0)) or 2 (i.e. Pd(II)). A wide variety ofsuch palladium-containing compounds and complexes are useful ascatalysts for the present method. Examples of palladium-containingcompounds and complexes useful as catalysts in the method of Scheme 3include PdCl₂(PPh₃)₂ (bis(triphenylphosphine)palladium (II) dichloride),Pd(PPh₃)₄ (tetrakis(triphenylphosphine)palladium(0)), Pd(C₅H₇O₂)₂(palladium(II) acetyl-acetonate), Pd₂(dba)₃(tris(dibenzylideneacetone)dipalladium(0)), and[1,1′-bis(diphenyl-phosphino)ferrocene]dichloropalladium(II). The methodof Scheme 3 is generally conducted in a liquid phase, and therefore tobe most effective the palladium catalyst preferably has good solubilityin the liquid phase. Useful solvents include, for example, ethers suchas 1,2-dimethoxyethane, amides such as N,N-dimethylacetamide, andnon-halogenated aromatic hydrocarbons such as toluene.

The method of Scheme 3 can be conducted over a wide range oftemperatures, ranging from about 25 to about 150° C. Of note aretemperatures from about 60 and about 110° C., which typically providefast reaction rates and high product yields. The general methods andprocedures for aminocarbonylation with an aryl bromide and an amine arewell known in the literature; see, for example, H. Horino et al.,Synthesis 1989, 715; and J. J. Li, G. W. Gribble, editors, Palladium inHeterocyclic Chemistry: A Guide for the Synthetic Chemist, ElsevierScience Ltd, 2000.

As shown in Scheme 4, compounds of Formula 1d (compounds of Formula 1wherein Q is Q-A and Z¹ is Z¹-2) wherein W⁵ is the same as W¹ can beprepared by the condensation of compounds of Formula 1c (Formula 1wherein Q is Q-A, Z¹ is Z¹-1, and R⁵ and R⁶ are H) wherein W¹ is O or Swith compounds of Formula 5 in the presence of condensing agents. Thereaction conditions are well illustrated in previous art; for example,see, T. Schmidt et al., WO2007/006670. Suitable condensing agentsinclude carboxylic acid anhydrides, dicyclohexylcarbodiimide, sulfurylchloride, phosphorus(V) oxide and phosphorus oxychloride.

As shown in Scheme 5, compounds of Formula 1e (Formula 1 wherein Q isQ-A, Z¹ is Z¹-3, and q is 1) wherein W⁶ is the same as W¹ can beprepared by treating the sulfoxides of Formula 6 with amino compounds ofFormula 7 using Rh₂(OAc)₄ as a catalyst in combination with iodobenzenediacetate and magnesium oxide. The general procedure is welldemonstrated in the literature, for example, see, H. Okamura & C. Bolm,Org. Lett., 2004, 6, 1305.

As shown in Scheme 6, compounds of Formula 6 can be prepared fromcompounds of Formula 8 by treatment with m-chloroperbenzoic acid(MCPBA). Oxidation of thioethers of Formula 8 with 1.0 equivalent ofMCPBA at low temperature, preferably at −78 to −40° C., provides thesulfoxides of Formula 6 in good yield. The compounds of Formula 8 can beprepared by the methods illustrated in Schemes 1, 2 and 3.

As shown in Scheme 7, compounds of Formula 1e-a (Formula 1 wherein Q isQ-A, Z¹ is Z¹-3, and q is 0) wherein W⁶ is the same as W¹ can beprepared from compounds of Formula 8 analogous to the method of Scheme 5using Rh₂(OAc)₄ as a catalyst in combination with iodobenzene diacetateand magnesium oxide.

As shown in Scheme 8, compounds of Formula 2 can be prepared byhydrolysis of the esters of Formula 9, wherein R^(a) is methyl or ethyl.In this method, compounds of Formula 9 are converted to thecorresponding carboxylic acids of Formula 2 by general procedures wellknown in the art. For example, treatment of a methyl or ethyl ester ofFormula 9 with aqueous lithium hydroxide in tetrahydrofuran, followed byacidification yields the corresponding carboxylic acid of Formula 2.

Alcohols of Formula 10 can substituted for the amines of Formula 3 inthe reaction of Scheme 3, to yield the esters of Formula 9 as shown inScheme 9.

As shown in Scheme 10, compounds of Formula 4 can be prepared by the1,3-dipolar cycloaddition of styrenes of Formula 12 with nitrile oxidesderived from oximes of Formula 11. This reaction typically proceedsthrough the intermediacy of an in situ generated hydroxamyl chloride,which is dehydrochlorinated to the nitrile oxide, which then undergoes1,3-dipolar cycloaddition with the styrene of Formula 12 to affordcompounds of Formula 4. In a typical procedure, a chlorinating reagentsuch as sodium hypochlorite, N-chlorosuccinimide, or chloramine-T iscombined with the oxime in the presence of the styrene. Depending on theconditions, amine bases such as pyridine or triethylamine may benecessary to facilitate the dehydrochlorination reaction. The reactioncan be run in a wide variety of solvents including tetrahydrofuran,diethyl ether, methylene chloride, dioxane, and toluene withtemperatures ranging from room temperature to the reflux temperature ofthe solvent. General procedures for cycloaddition of nitrile oxides witholefins are well documented in the chemical literature; for example, seeLee, Synthesis, 1982, 6, 508-509; Kanemasa et al., Tetrahedron, 2000,56, 1057-1064; EP 1,538,138-A1, as well as references cited within.

As shown in Scheme 11, the oximes of Formula 11 can be prepared by thereaction of aldehydes of Formula 13 with hydroxylamine according toknown literature procedures. For example, see, H. K. Jung et al. Bioorg.Med. Chem. 2004, 12, 3965.

As shown in Scheme 12, aldehydes of Formula 13 can be prepared bymethods known in art. For example, preparation of the compounds ofFormula 13, wherein Y¹—Y²—Y³ is —CH═CH—NH(R³)— or —NH(R³)—CH═CH—, isdisclosed by Lianhai Li et al. Tetrahedron Lett. 2003, 44, 5987. Thedibromo compounds of Formula 14, wherein Y¹—Y²—Y³ is —CH═CH—N(R³)—, area class of compounds reported in the chemical literature; for example,see, A. P. Dobbs et al. Synlett 1999, 10, 1594.

As shown in Scheme 13, aldehydes of Formula 13 can also be prepared frommethyl derivatives of Formula 15 by methods known in synthetic art, forexample, see, E. R. Mewshaw et al. WO2004/1303941. The compounds ofFormula 15, wherein Y¹—Y²—Y³ is —CH═CH—O—, —CH═CH—S—, —O—CH═CH—, or—S—CH═CH—, can be prepared by general methods known in the art; some arealso commercially available.

As shown in Scheme 14, compounds of Formula 1g (Formula 1 wherein Q isQ-B, Z² is Z²-1 or Z²-2 and W² or W³ are S) can be prepared by treatmentof corresponding amide compounds of Formula 1f (compounds of Formula 1wherein Q is Q-B, Z² is Z²-1 or Z²-2 and W² or W³ are O) with a thiotransfer reagent. The method of Scheme 14 is conducted as described forScheme 1.

As shown in Scheme 15, compounds of Formula 1f (Formula 1 wherein Q isQ-B, Z² is Z²-1 or Z²-2 and W² or W³ are O) can be prepared by couplingthe corresponding carboxylic acids of Formula 16 with appropriatelysubstituted amino compounds of Formula 17 or 18. The method of Scheme 15is conducted as described for Scheme 2.

As shown in Scheme 16, compounds of Formula 1f (Formula 1 wherein Q isQ-B, Z² is Z²-1 or Z²-2, and W² or W³ are O) can also be prepared byaminocarbonylation of aryl bromides of Formula 19 with appropriatelysubstituted amino compounds of Formula 17 or 18. The method of Scheme 16is conducted as described for Scheme 3.

As shown in Scheme 17, amides of Formula 1h (Formula 1 wherein Q is Q-Band Z² is Z²-3) can be prepared by coupling the corresponding acids ofFormula 20 with appropriately substituted amino compounds of Formula 21.Amide formation reactions are well known in the synthetic art. Treatingacids of Formula 20 with amino compounds of Formula 21 in the presenceof dehydrating reagents, such as carboxylic acid chlorides, DCC orpolymer-supported (PS)-carbodiimide, in an anhydrous aprotic solventsuch as dichloromethane provides compounds of Formula 1h. The method ofScheme 17 is illustrated in Step C of Example 1.

As shown in Scheme 18, amides of Formula 1h-a (Formula 1h wherein R¹¹ isH) can be prepared by the corresponding acids of Formula 20a (compoundsof Formula 20 wherein R¹¹ is H) through intermediates of Formula 22 andfurther reaction with the appropriately substituted amino compounds ofFormula 21. The cyclization reaction is typically carried out usingdehydrating reagents, such as polymer-supported (PS)-carbodiimide ordicyclohexyl carbodiimide (DCC) in an anhydrous aprotic solvent such asdichloromethane at room temperature. The intermediates of Formula 22 canbe used directly without any purification if polymer-supported DCC isused as the dehydrating reagent. The subsequent amide bond formation canbe achieved through mixing the intermediates of Formula 22 with aminocompounds of Formula 21 in N,N-dimethylformamide heated to a temperaturebetween 100 and 180° C. using microwave irradiation. The method ofScheme 18 is illustrated in Example 2.

As shown in Scheme 19, compounds of Formula 1i (Formula 1 wherein Q isQ-B and Z² is Z²-4) wherein W⁵ is O or S can be prepared by couplingcompounds of Formula 23 with compounds of Formula 5. The method ofScheme 19 is conducted as described for Scheme 4.

As shown in Scheme 20, compounds of Formula 1j (Formula 1 wherein Q isQ-B, Z² is Z²-5, and q is 1) wherein W⁵ is O or S can be prepared bytreating sulfoxides of Formula 25 with amines of Formula 7. The methodof Scheme 20 is conducted as described for Scheme 5 and is illustratedin Step C of Example 3.

As shown in Scheme 21, sulfoxides of Formula 25 can be prepared bytreating sulfides of Formula 26 with MCPBA. The method of Scheme 21 isconducted as described for Scheme 6 and is illustrated in Step B ofExample 3.

As shown in Scheme 22, compounds of Formula 1j-a (Formula 1 wherein Q isQ-B, Z² is Z²-5, and q is 0) can be prepared from sulfides of Formula 26and amines of Formula 7. The method of Scheme 22 is conducted asdescribed for Scheme 7.

As shown in Scheme 23, compounds of Formula 26a (Formula 26 wherein W⁶is O) can be prepared by coupling the acids of Formula 16 withappropriately substituted amino compounds of Formula 27. The method ofScheme 23 is conducted as described for Scheme 2 and is illustrated inStep A of Example 3.

As shown in Scheme 24, carboxylic acids of Formula 16 can be prepared byhydrolysis of the corresponding esters of Formula 28, wherein R^(a) ismethyl or ethyl. The method of Scheme 24 is conducted as described forScheme 8.

As shown in Scheme 25, compounds of Formula 28 can be prepared bycoupling of the corresponding bromides of Formula 19 with alcohols ofFormula 10, for example, methanol or ethanol, with carbon monoxide inthe presence of palladium catalysts. The method of Scheme 25 isconducted as described for Scheme 9.

As shown in Scheme 26, carboxylic acids of Formula 20 can be prepared byhydrolysis of the corresponding esters of Formula 29. The method ofScheme 26 is conducted as described for Scheme 8 and is illustrated inStep B of Example 1.

As shown in Scheme 27, compounds of Formula 29a (Formula 29 wherein W⁴is O) can be prepared by coupling bromides of Formula 19 withappropriately substituted amino compounds of Formula 30 (orcorresponding salts) in the presence of carbon monoxide. The method ofScheme 27 is conducted as described for Scheme 3 and is illustrated inStep A of Example 1.

As shown in Scheme 28, compounds of Formula 19 can be prepared by the1,3-dipolar cyclization of styrenes of Formula 12 with oximes of Formula31. The method of Scheme 28 is conducted as described for Scheme 10.

As shown in Scheme 29, oximes of Formula 31 can be prepared by reactionof the corresponding aldehydes of Formula 32 with hydroxylamine. Themethod of Scheme 29 is conducted as described for Scheme 11.

As shown in Scheme 30, aldehydes of Formula 32 can be prepared bytreating compounds of Formula 33 with n-BuLi at −78° C. and reacting thederived lithiated intermediate with N,N-dimethylformamide. The bromocompounds of Formula 33 can be prepared by general methods known inliterature, for example, see Synthesis, 2002, 83.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula 1 may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula 1. One skilled in the artwill also recognize that it may be necessary to perform a combination ofthe steps illustrated in the above schemes in an order other than thatimplied by the particular sequence presented to prepare the compounds ofFormula 1.

One skilled in the art will also recognize that compounds of Formula 1and the intermediates described herein can be subjected to variouselectrophilic, nucleophilic, radical, organometallic, oxidation, andreduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Steps in the following Examples illustrate a procedure foreach step in an overall synthetic transformation, and the startingmaterial for each step may not have necessarily been prepared by aparticular preparative run whose procedure is described in otherExamples or Steps. Percentages are by weight except for chromatographicsolvent mixtures or where otherwise indicated. Parts and percentages forchromatographic solvent mixtures are by volume unless otherwiseindicated. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane; “s” means singlet, “d” means doublet, “t” meanstriplet, “q” means quartet, “m” means multiplet, “dd” means doublet ofdoublets, “dt” means doublet of triplets and “br” means broad.

EXAMPLE 1 Preparation of4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-[2-methoxyethyl)amino]-2-oxoethyl]-1-naphthalenecarboxamideStep A:N-[[4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]carbonyl]glycinemethyl ester

A mixture of3-(4-bromo-1-naphthalenyl)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)isoxazole(500 mg), [1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II)(PdCl₂(dppf)) (82 mg), glycine methyl ester hydrochloride (514 mg) andtriethylamine (2.8 mL) in toluene (10 mL) in a vial was purged withcarbon monoxide for 15 minutes. The reaction vial was maintained withcarbon monoxide using a balloon. The reaction mixture was stirredovernight at 70° C. under carbon monoxide atmosphere. The mixture wascooled to room temperature, filtered through a short pad of Celite®diatomaceous filter aid and rinsed with small amount of ethyl acetate.The filtrate was concentrated, and the residue was purified by columnchromatography on silica gel using hexanes/ethyl acetate (4:1 to 1:1) aseluent to afford the title product as a white solid (310 mg, 58% yield).

¹H NMR (CDCl₃) δ 8.75 (d, 1H), 8.28 (d, 1H), 7.45-7.60 (m, 7H), 7.36 (d,1H), 6.78 (t, br., 1H), 4.26 (d, 2H), 4.21 (d, 1H), 3.87 (d, 1H), 3.80(s, 3H).

Step B:N-[[4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]carbonyl]glycine

To a stirred solution ofN-[[4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]carbonyl]glycinemethyl ester (i.e. the title product of Step A) (620 mg) intetrahydrofuran (5 mL) was added an aqueous solution of lithiumhydroxide (300 mg in 5 mL of water). After stirring at room temperaturefor 1 h, the reaction mixture was diluted with water and extracted withhexane. The aqueous layer was acidified with 6.0 N HCl to pH=2, causinga white precipitate to form. The aqueous mixture was extracted withethyl acetate, washed with brine, dried with anhydrous sodium sulfate,and concentrated to afford the title compound as a white solid (600 mg,99% yield).

¹H NMR (CD₃S(═O)CD₃) δ 9.02 (t, 1H), 8.81 (d, 1H), 8.37 (d, 1H), 7.92(d, 1H), 7.83 (t, 1H), 7.65-7.74 (m, 5H), 4.58 (d, 1H), 4.54 (d, 1H),4.02 (d, 2H).

Step C:4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-[2-methoxyethyl)amino]-2-oxoethyl]-1-naphthalenecarboxamide

To a stirred solution ofN-[[4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]carbonyl]glycine(i.e. the title product of Step B) (100 mg) and pyridine (0.019 mL) indichloromethane (3 mL) was added trimethylacetyl chloride (0.029 mL).The reaction mixture was stirred at room temperature for 2 h, and then2-methoxyethylamine (0.11 mL) and triethylamine (0.68 mL, 5.0 mmol) wereadded. The reaction mixture was stirred at room temperature overnight,quenched with water, extracted with dichloromethane, washed with brine,dried with anhydrous sodium sulfate and concentrated. The residue waspurified by column chromatography on silica gel using hexanes/ethylacetate (3:2 to 1:4) as eluent to afford the title compound, a compoundof the present invention, as a white solid (71 mg, 0.13 mmol, 65%yield).

¹H NMR (CDCl₃) δ 8.82 (d, 1H), 8.32 (d, 1H), 7.45-7.66 (m, 7H), 7.00 (brs, 1H), 6.45 (br s, 1H), 4.25 (d, 1H), 4.21 (d, 2H), 3.89 (d, 1H), 3.49(m, 4H), 3.36 (s, 3H).

EXAMPLE 2 Preparation ofN-[2-[(cyclopropylmethyl)amino]-2-oxoethyl]-4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamideStep A:2-[4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]-5(4H)-oxazolone

A mixture ofN-[[4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]carbonyl]glycine(510 mg) and PS (polymer supported)-carbodiimide (1.69 g, 123 mmol/g) indichloromethane (25 mL) was stirred at room temperature overnight. Thereaction mixture was filtered through a short pad of Celite®diatomaceous filter aid and rinsed with dichloromethane. The filtratewas concentrated to provide the title compound (400 mg, 81% yield) as apale yellow solid used directly for next step.

¹H NMR (CDCl₃) δ 9.33 (m, 1H), 8.87 (m, 1H), 8.15 (d, 1H), 7.73 (m, 2H),7.59 (d, 1H), 7.57 (d, 2H), 7.46 (dd, 1H), 4.62 (s, 2H), 4.29 (d, 1H),3.93 (d, 1H).

Step B:N-[2-[(cyclopropylmethyl)amino]-2-oxoethyl]-4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide

A mixture of2-[4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]-5(4H)-oxazolone(i.e. the title product of Step A) (50 mg) and (aminomethyl)cyclopropane(0.1 mL) in N,N-dimethylformamide (1 mL) was irradiated with microwaveradiation to maintain a temperature around 150° C. for 30 minutes. Thereaction mixture was diluted with water and extracted with ethylacetate. The organic layer was washed with brine, dried with anhydroussodium sulfate, and concentrated. The residue was purified by columnchromatography on silica gel using hexanes/ethyl acetate (3:2 to 3:7) aseluent to afford the title compound, a compound of the presentinvention, as a pale yellow solid (47 mg, 82% yield).

¹H NMR (CDCl₃) δ 8.83 (d, 1H), 8.31 (d, 1H), 7.45-7.67 (m, 7H), 7.10 (brs, 1H), 6.40 (br s, 1H), 4.25 (d, 1H), 4.21 (d, 2H), 3.89 (d, 1H), 3.17(dd, 2H), 0.97 (m, 1H), 0.52 (m, 2H), 0.21 (m, 2H).

EXAMPLE 3 Preparation of4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-[S-methyl-N-(2,2,2-trifluoroacetyl)sulfonimidoyl]ethyl]-1-naphthalenecarboxamideStep A:4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazol)]-N-[2-(methylthio)ethyl]-1-naphthalenecarboxamide

To a stirred suspension of4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxylicacid (620 mg) in dichloromethane (20 mL) at room temperature was addedoxalyl chloride (0.24 mL), followed by two drops ofN,N-dimethylformamide. The reaction mixture was stirred at roomtemperature for 1.5 h and then concentrated under vacuum. The residuewas dissolved in dichloromethane (10 mL) and added to a stirred solutionof 2-(methylthio)ethylamine (0.13 mL) and Et₃N (0.38 mL) indichloromethane (10 mL) at room temperature. The resulting reactionmixture was stirred at room temperature overnight. The reaction mixturewas quenched with water and extracted with dichloromethane, washed withbrine, dried with sodium sulfate and concentrated, and the residue waspurified by column chromatography on silica gel using hexanes/ethylacetate (7:3 to 1:1) as eluent to afford the title compound as a whitesolid (510 mg, 71% yield).

¹H NMR (CDCl₃) δ 8.78 (d, 1H), 8.27 (d, 1H), 7.56-7.64 (m, 4H), 7.49 (d,1H), 7.46 (dd, 1H), 7.40 (d, 1H), 6.57 (br t, 1H), 4.23 (d, 1H), 3.88(d, 1H), 3.71 (q, 2H), 2.79 (t, 2H), 2.15 (s, 3H).

Step B:4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-(methylsulfinyl)ethyl]-1-naphthalenecarboxamide

To a stirred solution of4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-(methylthio)ethyl]-1-naphthalenecarboxamide(i.e. the title product of Step A) (100 mg) in dichloromethane (10 mL)was added MCPBA (47 mg, 70%) at −78° C. The reaction mixture was stirredat −78 to −70° C. for 2.5 h, then quenched with saturated sodiumbicarbonate, extracted with dichloromethane, washed with brine, driedwith sodium sulfate, and concentrated to afford the title compound as awhite solid (102 mg, 99% yield).

¹H NMR (CDCl₃) δ 8.78 (d, 1H), 8.29 (d, 1H), 7.42-7.64 (m, 7H), 7.37 (brt, 1H), 4.23 (d, 1H), 4.00 (q, 2H), 3.88 (d, 1H), 3.18 (dt, 1H), 2.89(dt, 1H), 2.62 (s, 3H).

Step C:4-[5-(3,5-dichlorophenyl-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-(S-methyl-N-(2,2,2-trifluoroacetyl)sulfonimidoyl)ethyl]-1-naphthalenecarboxamide

To a stirred suspension of4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-(methylsulfinyl)ethyl]-1-naphthalenecarboxamide(i.e. the title product of Step B) (180 mg), 2,2,2-trifluoroacetamide(75 mg), MgO (53 mg), and Rh₂(OAc)₄ (4 mg) in dichloromethane (4 mL) wasadded PhI(OAc)₂ (160 mg) at room temperature. The resulting mixture wasstirred for 5 h at room temperature, then filtered through a short padof Celite® diatomaceous filter aid, and rinsed with ethyl acetate. Thefiltrate was concentrated, and the residue was purified by columnchromatography on silica gel using hexanes/ethyl acetate (3:7 to 1:9) aseluent to afford the title compound, a compound of the presentinvention, as yellow oil (100 mg, 46% yield).

¹H NMR (CDCl₃) δ 8.80 (d, 1H), 8.26 (d, 1H), 7.42-7.65 (m, 7H), 6.99 (brt, 1H), 4.24 (d, 1H), 4.11 (m, 2H), 3.89 (d, 1H), 3.82 (m, 2H), 3.48 (s,3H).

EXAMPLE 4 Preparation of4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-(S-methylsulfonimidoyl)ethyl]-1-naphthalenecarboxamide

To a stirred solution of4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-[S-methyl-N-(2,2,2-trifluoroacetyl)sulfonimidoyl]ethyl]-1-naphthalene-carboxamide(i.e. the title compound of Example 3) (60 mg) in methanol (4 mL) wasadded potassium carbonate (230 mg) at room temperature. After stirringfor 30 minutes at room temperature, the reaction mixture was filteredthrough a short pad of silical gel and rinsed with ethyl acetate. Afterconcentration, the residue was purified by column chromatography onsilica gel using dichloromethane/methanol (98:2 to 92:8) as eluent toprovide the title product, a compound of the present invention, as awhite solid (39 mg, 76% yield).

¹H NMR (CD₃COCD₃) δ 8.91 (d, 1H), 8.43 (d, 1H), 8.18 (br s, 1H), 7.87(d, 1H), 7.63-7.76 (m, 6H), 4.61 (d, 1H), 4.47 (d, 1H), 3.99 (m, 2H),3.50 (m, 2H), 3.35 (br s, 1H), 3.07 (s, 3H).

EXAMPLE 5 Preparation of4-[4,5-dihydro-5-(3,4,5-trichlorophenyl)-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-(S-methylsulfinimidoyl)ethyl]-1-naphthalenecarboxamideStep A:4-[4,5-dihydro-5-(3,4,5-trichlorophenyl)-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-[S-methyl-N-(2,2,2-trifluoroacetyl)sulfinimidoyl]ethyl]-1-naphthalenecarboxamide

To a stirred suspension of4-[4,5-dihydro-5-(3,4,5-trichlorophenyl)-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-(methylthio)ethyl]-1-naphthalenecarboxamide(prepared analogously as described for the compound of Example 3, StepA) (200 mg), 2,2,2-trifluoroacetamide (80 mg), MgO (57 mg), andRh₂(OAc)₄ (4 mg) in dichloromethane (4 mL) was added PhI(OAc)₂ (172 mg)at room temperature. The resulting mixture was stirred overnight at roomtemperature, then filtered through a short pad of Celite® diatomaceousfilter aid, and rinsed with ethyl acetate. The filtrate wasconcentrated, and the residue was purified by column chromatography onsilica gel using hexanes/ethyl acetates (1:1 to 1:4) as eluent to affordthe title compound as a semisolid (70 mg, 30% yield).

¹H NMR (CDCl₃) δ 8.77 (d, 1H), 8.31 (d, 1H), 7.70 (s, 2H), 7.54-7.66 (m,4H), 7.44 (d, 1H), 4.25 (d, 1H), 4.16 (m, 1H), 3.88 (d, 1H), 3.58 (m,2H), 3.22 (m, 1H), 2.87 (s, 3H).

Step B:4-[4,5-dihydro-5-(3,4,5-trichlorophenyl)-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-(S-methylsulfinimidoyl)ethyl]-1-naphthalenecarboxamide

To a stirred solution of4-[4,5-dihydro-5-(3,4,5-trichlorophenyl)-5-(trifluoromethyl)-3-isoxazolyl]-N-[2-[S-methyl-N-(2,2,2-trifluoroacetyl)sulfinimidoyl]ethyl]-1-naphthalene-carboxamide(70 mg) (i.e. the title compound of Step A) in methanol (2 mL) was addedpotassium carbonate (300 mg) at room temperature. After stirringovernight at room temperature, the reaction mixture was filtered througha short pad of silica gel and rinsed with ethyl acetate. Afterconcentration, the residue was purified by column chromatography onsilica gel using dichloromethane/methanol (98:2 to 92:8) as eluent toafford the title compound, a compound of the present invention, as asemisolid (9 mg, 15% yield).

¹H NMR (CDCl₃) δ 8.81 (d, 1H), 8.35 (d, 1H), 7.61-7.70 (m, 5H), 7.49 (d,1H), 7.11 (br t, 1H), 4.26 (d, 1H), 4.11 (m, 2H), 3.88 (d, 1H), 3.24 (m,1H), 2.95 (m, 1H), 2.70 (s, 3H).

EXAMPLE 6 Preparation of4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-(dimethyl-λ⁴-sulfanylidene)-1-naphthalenecarboxamide

To a stirred solution of dimethylsulfoxide (38 mg) in dichloromethane (1mL) at −60° C. was added trifluoroacetic anhydride (105 mg). After thereaction mixture was stirred for 10 minutes at −60° C., a solution of4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide(75 mg, in 1.5 mL of dichloromethane and 0.4 mL of dimethylsulfoxide)was added. The reaction mixture was allowed to warm to −20° C. over 1 h,then quenched with water and extracted with dichloromethane. Thecombined organic extract was washed with aqueous 1.0 N of NaOH andbrine, dried with anhydrous sodium sulfate and concentrated. The residuewas purified by column chromatography on silica gel usingdichloromethane/methanol (98:2 to 95:5) as eluent to afford the titleproduct, a compound of the present invention, as semi-solid (70 mg, 82%yield).

¹H NMR (CDCl₃) δ 8.80 (m, 1H), 8.69 (m, 1H), 7.85 (d, 1H), 7.44-7.62 (m,6H), 4.26 (d, 1H), 3.89 (d, 1H), 2.86 (s, 6H).

By the procedures described herein together with methods known in theart, the following compounds of Tables 1 to 52 can be prepared. Thefollowing abbreviations are used in the Tables which follow: Cmpd. meanscompound, n means normal, i means iso, c means cyclo, Me means methyl,Et means ethyl, Pr means propyl, i-Pr means isopropyl, Ph means phenyl,OMe means methoxy, SMe means methylthio, CN means cyano, Ph meansphenyl, Py means pyridinyl, S(═O)Me means methylsulfinyl, and SO₂Memeans methylsulfonyl. In the Tables the variable “R²” represents one ora combination of substituents as defined.

In Table 49, compounds are specifically named by first indicating therelevant preceding Table number (i.e. from Tables 1-48) defining aMarkush structure and then the line number for the preceding Tabledefining substituents attached to the Markush structure. Each suchdesignation specifically identifies a unique compound of the presentinvention. For example, Compound I-1 is the compound of Formula 1, asdefined by Table 1, Line 1 wherein A is phenyl, Q is Q-A-1, R² is 3-CF₃,R⁵ is Et and R⁶ is H. Similarly, Compound 17-4 is the compound ofFormula 1, Table 17, Line 4 wherein A is phenyl, Q is Q-A-17, R² is3-Cl, 5-Cl, R¹⁹ is Et and R²⁰ is H.

TABLES 1-8

Q is:

Q-A-1 Table 1

Q-A-2 Table 2

Q-A-3 Table 3

Q-A-4 Table 4

Q-A-5 Table 5

Q-A-6 Table 6

Q-A-7 Table 7

Q-A-8 Table 8 Line R⁵ R⁶ wherein R² is 3-CF₃ 1 Et H 2 CH₂-c-Py H 3CH₂-c-Pr H 4 CH₂CF₃ H 5 CH₂CH₂OMe H 6 CH₂CH₂SMe H 7 CH₂CH₂(S═O)Me H 8CH₂CH₂SO₂Me H 9 CH₂C(═O)NHCH₃ H 10 CH₂C(═O)NHCH₂CH₃ H 11 CH₂C(═O)NH-c-PrH 12 CH₂C(═O)NHCH₂CF₃ H 13 CH(CH₃)C(═O)NHCH₂CF₃ H 14 CH₂C(═O)NH(CH₂)₂OMeH 15 CH₂C(═O)NH(CH₂)₂SMe H wherein R² is 3-Br, 5-Br 16 Et H 17 CH₂-2-PyH 18 CH₂-c-Pr H 19 CH₂CF₃ H 20 CH₂CH₂OMe H 21 CH₂CH₂SMe H 22CH₂CH₂(S═O)Me H 23 CH₂CH₂SO₂Me H 24 CH₂C(═O)NHCH₃ H 25 CH₂C(═O)NHCH₂CH₃H 26 CH₂C(═O)NH-c-Pr H 27 CH₂C(═O)NHCH₂CF₃ H 28 CH(CH₃)C(═O)NHCH₂CF₃ H29 CH₂C(═O)NH(CH₂)₂OMe H 30 CH₂C(═O)NH(CH₂)₂SMe H wherein R² is 3-Cl,4-F, 5-Cl 31 Et H 32 CH₂-2-Py H 33 CH₂-c-Pr H 34 CH₂CF₃ H 35 CH₂CH₂OMe H36 CH₂CH₂SMe H 37 CH₂CH₂(S═O)Me H 38 CH₂CH₂SO₂Me H 39 CH₂C(═O)NHCH₃ H 40CH₂C(═O)NHCH₂CH₃ H 41 CH₂C(═O)NH-c-Pr H 42 CH₂C(═O)NHCH₂CF₃ H 43CH(CH₃)C(═O)NHCH₂CF₃ H 44 CH₂C(═O)NH(CH₂)₂OMe H 45 CH₂C(═O)NH(CH₂)₂SMe Hwherein R² is 3-Cl, 5-Cl 46 CH₂CF₃ Me 47 CH₂-2-Py Me 48 CH₂CH₂SMe Me 49CH₂CH₂S(═O)Me Me 50 CH₂CH₂SO₂Me Me 51 CH₂C(═O)NHCH₂CF₃ Me 52CH(CH₃)C(═O)NHCH₂CF₃ Me 53 CH₂CF₃ C(═O)Me 54 CH₂-2-Py C(═O)Me 55CH₂CH₂SMe C(═O)Me 56 CH₂CH₂S(═O)Me C(═O)Me 57 CH₂CH₂SO₂Me C(═O)Me 58CH₂C(═O)NHCH₂CF₃ C(═O)Me 59 CH(CH₃)C(═O)NHCH₂CF₃ C(═O)Me 60 CH₂CF₃ CO₂Me61 CH₂-2-Py CO₂Me 62 CH₂CH₂SMe CO₂Me 63 CH₂CH₂S(═O)Me CO₂Me 64CH₂CH₂SO₂Me CO₂Me 65 CH₂C(═O)NHCH₂CF₃ CO₂Me 66 CH(CH₃)C(═O)NHCH₂CF₃CO₂Me wherein R² is 3-Cl 67 CH₂CF₃ H 68 CH₂-2-Py H 69 CH₂CH₂SMe H 70CH₂-c-Pr H 71 CH₂C(═O)NHCH₂CF₃ H wherein R² is 3-Br, 5-OCF₃ 72 CH₂CF₃ H73 CH₂-2-Py H 74 CH₂CH₂SMe H 75 CH₂-c-Pr H 76 CH₂C(═O)NHCH₂CF₃ H whereinR² is 3-Cl, 5-Br 77 CH₂CF₃ H 78 CH₂-2-Py H 79 CH₂CH₂SMe H 80 CH₂-c-Pr H81 CH₂C(═O)NHCH₂CF₃ H wherein R² is 3-CF₃, 5-Cl 82 CH₂CF₃ H 83 CH₂-2-PyH 84 CH₂CH₂SMe H 85 CH₂-c-Pr H 86 CH₂C(═O)NHCH₂CF₃ H wherein R² is 3-Cl,4-CN, 5-Cl 87 CH₂CF₃ H 88 CH₂-2-Py H 89 CH₂CH₂SMe H 91 CH₂-c-Pr H 92CH₂C(═O)NHCH₂CF₃ H wherein R² is 3-Cl, 5-Cl 93 Et H 94 CH₂-2-Py H 95CH₂-c-Pr H 96 CH₂CF₃ H 97 CH₂CH₂OMe H 98 CH₂CH₂SMe H 99 CH₂CH₂(S═O)Me H100 CH₂CH₂SO₂Me H 101 CH₂C(═O)NHCH₃ H 102 CH₂C(═O)NHCH₂CH₃ H 103CH₂C(═O)NH-c-Pr H 104 CH₂C(═O)NHCH₂CF₃ H 105 CH(CH₃)C(═O)NHCH₂CF₃ H 106CH₂C(═O)NH(CH₂)₂OMe H 107 CH₂C(═O)NH(CH₂)₂SMe H wherein R² is 3-Cl,4-Cl, 5-Cl 108 Et H 109 CH₂-2-Py H 110 CH₂-c-Pr H 111 CH₂CF₃ H 112CH₂CH₂OMe H 113 CH₂CH₂SMe H 114 CH₂CH₂(S═O)Me H 115 CH₂CH₂SO₂Me H 116CH₂C(═O)NHCH₃ H 117 CH₂C(═O)NHCH₂CH₃ H 118 CH₂C(═O)NH-c-Pr H 119CH₂C(═O)NHCH₂CF₃ H 120 CH(CH₃)C(═O)NHCH₂CF₃ H 121 CH₂C(═O)NH(CH₂)₂OMe H122 CH₂C(═O)NH(CH₂)₂SMe H wherein R² is 3-CF₃, 5-CF₃ 123 Et H 124CH₂-2-Py H 125 CH₂-c-Pr H 126 CH₂CF₃ H 127 CH₂CH₂OMe H 128 CH₂CH₂SMe H129 CH₂CH₂(S═O)Me H 130 CH₂CH₂SO₂Me H 131 CH₂C(═O)NHCH₃ H 132CH₂C(═O)NHCH₂CH₃ H 133 CH₂C(═O)NH-c-Pr H 134 CH₂C(═O)NHCH₂CF₃ H 135CH(CH₃)C(═O)NHCH₂CF₃ H 136 CH₂C(═O)NH(CH₂)₂OMe H 137 CH₂C(═O)NH(CH₂)₂SMeH wherein R² is 3-Br, 5-Br 138 CH₂CF₃ Me 139 CH₂-2-Py Me 140 CH₂CH₂SMeMe 141 CH₂CH₂S(═O)Me Me 142 CH₂CH₂SO₂Me Me 143 CH₂C(═O)NHCH₂CF₃ Me 144CH(CH₃)C(═O)NHCH₂CF₃ Me 145 CH₂CF₃ C(═O)Me 146 CH₂-2-Py C(═O)Me 147CH₂CH₂SMe C(═O)Me 148 CH₂CH₂S(═O)Me C(═O)Me 149 CH₂CH₂SO₂Me C(═O)Me 150CH₂C(═O)NHCH₂CF₃ C(═O)Me 151 CH(CH₃)C(═O)NHCH₂CF₃ C(═O)Me 152 CH₂CF₃CO₂Me 153 CH₂-2-Py CO₂Me 154 CH₂CH₂SMe CO₂Me 155 CH₂CH₂S(═O)Me CO₂Me 156CH₂CH₂SO₂Me CO₂Me 157 CH₂C(═O)NHCH₂CF₃ CO₂Me 158 CH(CH₃)C(═O)NHCH₂CF₃CO₂Me wherein R² is 3-Br 159 CH₂CF₃ H 160 CH₂-2-Py H 162 CH₂CH₂SMe H 163CH₂-c-Pr H 164 CH₂C(═O)NHCH₂CF₃ H wherein R² is 3-CF₃, 5-CF₃ 165 CH₂CF₃H 166 CH₂-2-Py H 167 CH₂CH₂SMe H 168 CH₂-c-Pr H 169 CH₂C(═O)NHCH₂CF₃ Hwherein R² is 3-CF₃, 5-F 170 CH₂CF₃ H 171 CH₂-2-Py H 172 CH₂CH₂SMe H 173CH₂-c-Pr H 174 CH₂C(═O)NHCH₂CF₃ H wherein R² is 3-CF₃, 5-Br 175 CH₂CF₃ H176 CH₂-2-Py H 177 CH₂CH₂SMe H 178 CH₂-c-Pr H 179 CH₂C(═O)NHCH₂CF₃ Hwherein R² is 3-Cl, 4-Me, 5-Cl 180 CH₂CF₃ H 181 CH₂-2-Py H 182 CH₂CH₂SMeH 183 CH₂-c-Pr H 184 CH₂C(═O)NHCH₂CF₃ H

TABLES 9-16

Q is:

Q-A-9 Table 9

Q-A-10 Table 10

Q-A-11 Table 11

Q-A-12 Table 12

Q-A-13 Table 13

Q-A-14 Table 14

Q-A-14 Table 15

Q-A-16 Table 16 Line R² R¹⁶ R¹⁷  1 3-Cl, 5-Cl Me Me  2 3-Cl, 5-Cl Et Me 3 3-Cl, 5-Cl n-Pr Me  4 3-Cl, 5-Cl Et Et  5 3-Cl, 5-Cl i-Pr i-Pr  63-Br, 5-Br Me Me  7 3-Br, 5-Br Et Me  8 3-Br, 5-Br n-Pr Me  9 3-Br, 5-BrEt Et 10 3-Br, 5-Br i-Pr i-Pr 11 3-Cl, 4-Cl, 5-Cl Me Me 12 3-Cl, 4-Cl,5-Cl Et Me 13 3-Cl, 4-Cl, 5-Cl n-Pr Me 14 3-Cl, 4-Cl, 5-Cl Et Et 153-Cl, 4-Cl, 5-Cl i-Pr i-Pr 16 3-Cl, 4-F, 5-Cl Me Me 17 3-Cl, 4-F, 5-ClEt Me 18 3-Cl, 4-F, 5-Cl n-Pr Me 19 3-Cl, 4-F, 5-Cl Et Et 20 3-Cl, 4-F,5-Cl i-Pr i-Pr 21 3-Cl Me Me 22 3-Cl Et Me 23 3-Cl n-Pr Me 24 3-Cl Et Et25 3-Cl i-Pr i-Pr 26 3-Br Me Me 27 3-Br Et Me 28 3-Br n-Pr Me 29 3-Br EtEt 30 3-Br i-Pr i-Pr 31 3-CF₃, 5-CF₃ Me Me 32 3-CF₃, 5-CF₃ Et Me 333-CF₃, 5-CF₃ n-Pr Me 34 3-CF₃, 5-CF₃ Et Et 35 3-CF₃, 5-CF₃ i-Pr i-Pr 363-CF₃, 5-Cl Me Me 37 3-CF₃, 5-Cl Et Me 38 3-CF₃, 5-Cl n-Pr Me 39 3-CF₃,5-Cl Et Et 40 3-CF₃, 5-Cl i-Pr i-Pr 41 3-CF₃, 5-Br Me Me 42 3-CF₃, 5-BrEt Me 43 3-CF₃, 5-Br n-Pr Me 44 3-CF₃, 5-Br Et Et 45 3-CF₃, 5-Br i-Pri-Pr 46 3-Cl, 4-CN, 5-Cl Me Me 47 3-Cl, 4-CN, 5-Cl Et Me 48 3-Cl, 4-CN,5-Cl n-Pr Me 49 3-Cl, 4-CN, 5-Cl Et Et 50 3-Cl, 4-CN, 5-Cl i-Pr i-Pr 513-Cl, 4-Me, 5-Cl Me Me 52 3-Cl, 4-Me, 5-Cl Et Me 53 3-Cl, 4-Me, 5-Cln-Pr Me 54 3-Cl, 4-Me, 5-Cl Et Et 55 3-Cl, 4-Me, 5-Cl i-Pr i-Pr 56 3-CF₃Me H 57 3-CF₃ Me C(═O)CF₃ 58 3-CF₃ Me CN 59 3-CF₃ Et H 60 3-CF₃ EtC(═O)CF₃

TABLES 17-24

Q is:

Q-A-17 Table 17

Q-A-18 Table 18

Q-A-19 Table 19

Q-A-20 Table 20

Q-A-21 Table 21

Q-A-22 Table 22

Q-A-23 Table 23

Q-A-24 Table 24 Line R² R¹⁹ R²⁰  1 3-Cl, 5-Cl Me H  2 3-Cl, 5-Cl MeC(═O)CF₃  3 3-Cl, 5-Cl Me CN  4 3-Cl, 5-Cl Et H  5 3-Cl, 5-Cl EtC(═O)CF₃  6 3-Br, 5-Br Me H  7 3-Br, 5-Br Me C(═O)CF₃  8 3-Br, 5-Br MeCN  9 3-Br, 5-Br Et H 10 3-Br, 5-Br Et C(═O)CF₃ 11 3-Cl, 4-Cl, 5-Cl Me H12 3-Cl, 4-Cl, 5-Cl Me C(═O)CF₃ 13 3-Cl, 4-Cl, 5-Cl Me CN 14 3-Cl, 4-Cl,5-Cl Et H 15 3-Cl, 4-Cl, 5-Cl Et C(═O)CF₃ 16 3-Cl, 4-F, 5-Cl Me H 173-Cl, 4-F, 5-Cl Me C(═O)CF₃ 18 3-Cl, 4-F, 5-Cl Me CN 19 3-Cl, 4-F, 5-ClEt H 20 3-Cl, 4-F, 5-Cl Et C(═O)CF₃ 21 3-Cl Me H 22 3-Cl Me C(═O)CF₃ 233-Cl Me CN 24 3-Cl Et H 25 3-Cl Et C(═O)CF₃ 26 3-Br Me H 27 3-Br MeC(═O)CF₃ 28 3-Br Me CN 29 3-Br Et H 30 3-Br Et C(═O)CF₃ 31 3-CF₃, 5-CF₃Me H 32 3-CF₃, 5-CF₃ Me C(═O)CF₃ 33 3-CF₃, 5-CF₃ Me CN 34 3-CF₃, 5-CF₃Et H 35 3-CF₃, 5-CF₃ Et C(═O)CF₃ 36 3-CF₃, 5-Cl Me C(═O)CF₃ 37 3-CF₃,5-Cl Me CN 38 3-CF₃, 5-Cl Me H 39 3-CF₃, 5-Cl Et C(═O)CF₃ 40 3-CF₃, 5-ClEt i-Pr 41 3-CF₃, 5-Br Me H 42 3-CF₃, 5-Br Me C(═O)CF₃ 43 3-CF₃, 5-Br MeCN 44 3-CF₃, 5-Br Et H 45 3-CF₃, 5-Br Et C(═O)CF₃ 46 3-Cl, 4-CN, 5-Cl MeH 47 3-Cl, 4-CN, 5-Cl Me C(═O)CF₃ 48 3-Cl, 4-CN, 5-Cl Me CN 49 3-Cl,4-CN, 5-Cl Et H 50 3-Cl, 4-CN, 5-Cl Et C(═O)CF₃ 51 3-Cl, 4-Me, 5-Cl Me H52 3-Cl, 4-Me, 5-Cl Me C(═O)CF₃ 53 3-Cl, 4-Me, 5-Cl Me CN 54 3-Cl, 4-Me,5-Cl Et H 55 3-Cl, 4-Me, 5-Cl Et C(═O)CF₃ 56 3-CF₃ Me H 57 3-CF₃ MeC(═O)CF₃ 58 3-CF₃ Me CN 59 3-CF₃ Et H 60 3-CF₃ Et C(═O)CF₃

TABLES 25-32

Line Y⁴ R⁷ R⁸ 1 CH H CH₂CH₂OCH₂CF₃ 2 CH H CH₂CH₂OCH₂CH₂OPh 3 CH HCH₂CH₂OCH₂CH₂OMe 4 CH H CH₂CH₂OCH₂CH₂SH 5 CH H CH₂CH₂OCH₂CH₂SMe 6 CH HCH₂CH₂OCH₂CH₂S(═O)Me 7 CH H CH₂CH₂OCH₂CH₂SO₂Me 8 CH HCH₂CH₂OCH₂CH₂SO₂NHMe 9 CH H CH₂CH₂O(CH₂)2SO₂N(Me)₂ 10 CH H(CH₂)₂O(CH₂)₂OC(═O)NHMe 11 CH H (CH₂)₂O(CH₂)₂OC(═O)N(Me)₂ 12 CH HCH₂CH₂OCH₂CH₂OCO₂Me 13 CH H CH₂CH₂OCH₂OCO₂Me 14 CH H CH₂CH₂OCH₂C(═O)NHMe15 CH H CH₂CH₂NHCH₂CF₃ 16 CH H CH₂CH₂N(Me)CH₂CF₃ 17 CH HCH₂CH₂N═CH-(2-Py) 18 CH H CH₂CH₂N═CH-(3-Py) 19 CH H CH₂CH₂NHC(═O)Me 20CH H CH₂CH₂SCN 21 CH H CH₂Si(Me)₃ 22 CH H CH₂Si(Me)₂Ph 23 CH HCH₂Si(Me)₂Et 24 CH H CH₂C(═O)OCH₂CH₂OMe 25 CH H CH₂C(═O)OCH₂CH₂OEt 26 CHH CH₂C(═S)SMe 27 CH H CH₂C(═S)OMe 28 CH H CH₂C(═O)SMe 29 CH H CH₂C(═S)Me30 CH H CH₂C(═S)N(Me)₂ 31 CH H CH₂C(═S)NHMe 32 CH H CH₂C(═S)NHCH₂CF₃ 33CH H CH₂P(═O)(OMe)₂ 34 CH H CH₂P(═S)(OMe)₂ 35 CH Me (CH₂)₂O(CH₂)₂SMe 36CH Me (CH₂)₂O(CH₂)₂S(═O)Me 37 CH Me (CH₂)₂O(CH₂)₂SO₂Me 38 CH C(═O)Me(CH₂)₂O(CH₂)₂SMe 39 CH C(═O)Me (CH₂)₂O(CH₂)₂S(═O)Me 40 CH C(═O)Me(CH₂)₂O(CH₂)₂SO₂Me 41 N H CH₂CH₂OCH₂CF₃ 42 N H CH₂CH₂OCH₂CH₂OPh 43 N HCH₂CH₂OCH₂CH₂OMe 44 N H CH₂CH₂OCH₂CH₂SH 45 N H CH₂CH₂OCH₂CH₂SMe 46 N HCH₂CH₂OCH₂CH₂S(═O)Me 47 N H CH₂CH₂OCH₂CH₂SO₂Me 48 N HCH₂CH₂OCH₂CH₂SO₂NHMe 49 N H CH₂CH₂O(CH₂)₂SO₂N(Me)₂ 50 N H(CH₂)₂O(CH₂)₂OC(═O)NHMe 51 N H (CH₂)₂O(CH₂)₂OC(═O)N(Me)₂ 52 N HCH₂CH₂OCH₂CH₂OCO₂Me 53 N H CH₂CH₂OCH₂OCO₂Me 54 N H CH₂CH₂OCH₂C(═O)NHMe55 N H CH₂CH₂NHCH₂CF₃ 56 N H CH₂CH₂N(Me)CH₂CF₃ 57 N H CH₂CH₂N═CH-(2-Py)58 N H CH₂CH₂N═CH-(3-Py) 59 N H CH₂CH₂NHC(═O)Me 60 N H CH₂CH₂SCN 61 N HCH₂Si(Me)₃ 62 N H CH₂Si(Me)₂Ph 63 N H CH₂Si(Me)₂Et 64 N HCH₂C(═O)OCH₂CH₂OMe 65 N H CH₂C(═O)OCH₂CH₂OEt 66 N H CH₂C(═S)SMe 67 N HCH₂C(═S)OMe 68 N H CH₂C(═O)SMe 69 N H CH₂C(═S)Me 70 N H CH₂C(═S)N(Me)₂71 N H CH₂C(═S)NHMe 72 N H CH₂C(═S)NHCH₂CF₃ 73 N H CH₂P(═O)(OMe)₂ 74 N HCH₂P(═S)(OMe)₂ 75 CH CO₂Me (CH₂)₂O(CH₂)₂SMe 76 CH CO₂Me(CH₂)₂O(CH₂)₂S(═O)Me 77 CH CO₂Me (CH₂)₂O(CH₂)₂SO₂Me 78 CH Et(CH₂)₂O(CH₂)₂SMe 79 CH Et (CH₂)₂O(CH₂)₂S(═O)Me 80 CH Et(CH₂)₂O(CH₂)₂SO₂Me A is:

TABLES 33-40

Line Y⁴ R⁹ R¹⁰ 1 CH H CN 2 CH H SO₂Me 3 CH H SO₂Ph 4 CH H SO₂N(Me)₂ 5 CHH NHMe 6 CH H N(Me)₂ 7 CH H C(═O)CF₃ 8 CH H CO₂CH₂CF₃ 9 CH H C(═O)N(Me)₂10 CH H C(═O)NHMe 11 CH CH₂CF₃ CN 12 CH CH₂CF₃ SO₂Me 13 CH CH₂CF₃ SO₂Ph14 CH CH₂CF₃ SO₂N(Me)₂ 15 CH CH₂CF₃ NHMe 16 CH CH₂CF₃ N(Me)₂ 17 CHCH₂CF₃ C(═O)CF₃ 18 CH CH₂CF₃ CO₂CH₂CF₃ 19 CH CH₂CF₃ C(═O)N(Me)₂ 20 CHCH₂CF₃ C(═O)NHMe 21 CH CH₂-2-Py CN 22 CH CH₂-2-Py SO₂Me 23 CH CH₂-2-PySO₂Ph 24 CH CH₂-2-Py SO₂N(Me)₂ 25 CH CH₂-2-Py NHMe 26 CH CH₂-2-Py N(Me)₂27 CH CH₂-2-Py C(═O)CF₃ 28 CH CH₂-2-Py CO₂CH₂CF₃ 29 CH CH₂-2-PyC(═O)N(Me)₂ 30 CH CH₂-2-Py C(═O)NHMe 31 N CH₂CF₃ CH₂OMe 32 N CH₂-2-PyCH₂OMe 33 N CH₂CH₂SMe CH₂OMe 34 N CH₂CH₂SO₂Me CH₂OMe 35 N CH₂CH₂S(═O)MeCH₂OMe 36 N Et CN 37 N Et SO₂Me 38 N Et SO₂Ph 39 N Et SO₂N(Me)₂ 40 N EtNHMe 41 N Et N(Me)₂ 42 CH H C(═O)CF₃ 43 N Et CO₂CH₂CF₃ 44 N EtC(═O)N(Me)₂ 45 N Et C(═O)NHMe 46 CH CH₂-c-Pr CN 47 CH CH₂-c-Pr SO₂Me 48CH CH₂-c-Pr SO₂Ph 49 CH CH₂-c-Pr SO₂N(Me)₂ 50 CH CH₂-c-Pr NHMe 51 CHCH₂-c-Pr N(Me)₂ 52 CH CH₂-c-Pr C(═O)CF₃ 53 CH CH₂-c-Pr CO₂CH₂CF₃ 54 CHCH₂-c-Pr C(═O)N(Me)₂ 55 CH CH₂-c-Pr C(═O)NHMe 56 N CH₂CH₂SMe CN 57 NCH₂CH₂SMe SO₂Me 58 N CH₂CH₂SMe SO₂Ph 59 N CH₂CH₂SMe SO₂N(Me)₂ 60 NCH₂CH₂SMe NHMe 61 N CH₂CH₂SMe N(Me)₂ 62 N CH₂CH₂SMe C(═O)CF₃ 63 NCH₂CH₂SMe CO₂CH₂CF₃ 64 N CH₂CH₂SMe C(═O)N(Me)₂ 65 N CH₂CH₂SMe C(═O)NHMe66 N CH₂CF₃ CH₂CO₂Me 67 N CH₂-2-Py CH₂CO₂Me 68 N CH₂CH₂SMe CH₂CO₂Me 69 NCH₂CH₂SO₂Me CH₂CO₂Me 70 N CH₂CH₂S(═O)Me CH₂CO₂Me A is:

TABLES 41-48

Line R¹¹ R¹² R¹³ R¹⁴ R¹⁵ 1 H H H H CH₂Ph 2 H H H H CH₂-2-Py 3 H H H HCH₂-3-Py 4 H H H H CH₂CH₂OH 5 H H H H CH(CH₃)CH₂OH 6 H H H HC(CH₃)₂CH₂OH 7 H H H H CH₂CH₂OMe 8 H H H H CH(CH₃)CH₂OMe 9 H H H HC(CH₃)₂CH₂OMe 10 H H H H CH₂CH₂SMe 11 H H H H CH₂CH₂S(═O)Me 12 H H H HCH₂CH₂SO₂Me 13 H H H H CH(Me)CH₂SMe 14 H H H H CHMeCH₂S(═O)Me 15 H H H HCH(Me)CH₂SO₂Me 16 H H H H C(Me)₂CH₂SMe 17 H H H H C(Me)₂CH₂S(═O)Me 18 HH H H C(Me)₂CH₂SO₂Me 19 H H H H CH₂C(═O)NHMe 20 H H H H CH₂C(═O)N(Me)₂21 H H H H CH₂C(═O)NHEt 22 H H H H CH₂C(═O)NH-c-Pr 23 H H H HCH₂C(═O)NHCH₂CF₃ 24 Me H H H CH₂Ph 25 Me H H H CH₂-2-Py 26 Me H H HCH₂-3-Py 27 Me H H H CH₂CH₂OH 28 Me H H H CH(CH₃)CH₂OH 29 Me H H HC(CH₃)₂CH₂OH 30 Me H H H CH₂CH₂OMe 31 Me H H H CH(CH₃)CH₂OMe 32 Me H H HC(CH₃)₂CH₂OMe 33 Me H H H CH₂CH₂SMe 34 Me H H H CH₂CH₂S(═O)Me 35 Me H HH CH₂CH₂SO₂Me 36 Me H H H CH(Me)CH₂SMe 37 Me H H H CHMeCH₂S(═O)Me 38 MeH H H CH(Me)CH₂SO₂Me 39 Me H H H C(Me)₂CH₂SMe 40 Me H H HC(Me)₂CH₂S(═O)Me 41 Me H H H C(Me)₂CH₂SO₂Me 42 Me H H H CH₂C(═O)NHMe 43Me H H H CH₂C(═O)N(Me)₂ 44 Me H H H CH₂C(═O)NHEt 45 Me H H HCH₂C(═O)NH-c-Pr 46 Me H H H CH₂C(═O)NHCH₂CF₃ 47 H H H Me CH₂Ph 48 H H HMe CH₂-2-Py 49 H H H Me CH₂-3-Py 50 H H H Me CH₂CH₂OH 51 H H H MeCH(CH₃)CH₂OH 52 H H H Me C(CH₃)₂CH₂OH 53 H H H Me CH₂CH₂OMe 54 H H H MeCH(CH₃)CH₂OMe 55 H H H Me C(CH₃)₂CH₂OMe 56 H H H Me CH₂CH₂SMe 57 H H HMe CH₂CH₂S(═O)Me 58 H H H Me CH₂CH₂SO₂Me 59 H H H Me CH(Me)CH₂SMe 60 H HH Me CHMeCH₂S(═O)Me 61 H H H Me CH(Me)CH₂SO₂Me 62 H H H Me C(Me)₂CH₂SMe63 H H H Me C(Me)₂CH₂S(═O)Me 64 H H H Me C(Me)₂CH₂SO₂Me 65 H H H MeCH₂C(═O)NHMe 66 H H H Me CH₂C(═O)N(Me)₂ 67 H H H Me CH₂C(═O)NHEt 68 H HH Me CH₂C(═O)NH-c-Pr 69 H H H Me CH₂C(═O)NHCH₂CF₃ 70 H Me H H CH₂Ph 71 HMe H H CH₂-2-Py 72 H Me H H CH₂-3-Py 73 H Me H H CH₂CH₂OH 74 H Me H HCH(CH₃CH₂OH 75 H Me H H C(CH₃)₂CH₂OH 76 H Me H H CH₂CH₂OMe 77 H Me H HCH(CH₃)CH₂OMe 78 H Me H H C(CH₃)₂CH₂OMe 79 H Me H H CH₂CH₂SMe 80 H Me HH CH₂CH₂S(═O)Me 81 H Me H H CH₂CH₂SO₂Me 82 H Me H H CH(Me)CH₂SMe 83 H MeH H CHMeCH₂S(═O)Me 84 H Me H H CH(Me)CH₂SO₂Me 85 H Me H H C(Me)₂CH₂SMe86 H Me H H C(Me)₂CH₂S(═O)Me 87 H Me H H C(Me)₂CH₂SO₂Me 88 H Me H HCH₂C(═O)NHMe 89 H Me H H CH₂C(═O)N(Me)₂ 90 H Me H H CH₂C(═O)NHEt 91 H MeH H CH₂C(═O)NH-c-Pr 92 H Me H H CH₂C(═O)NHCH₂CF₃ 93 H Me Me H CH₂Ph 94 HMe Me H CH₂-2-Py 95 H Me Me H CH₂-3-Py 96 H Me Me H CH₂CH₂OH 97 H Me MeH CH(CH₃)CH₂OH 98 H Me Me H C(CH₃)₂CH₂OH 99 H Me Me H CH₂CH₂OMe 100 H MeMe H CH(CH₃)CH₂OMe 101 H Me Me H C(CH₃)₂CH₂OMe 102 H Me Me H CH₂CH₂SMe103 H Me Me H CH₂CH₂S(═O)Me 104 H Me Me H CH₂CH₂SO₂Me 105 H Me Me HCH(Me)CH₂SMe 106 H Me Me H CHMeCH₂S(═O)Me 107 H Me Me H CH(Me)CH₂SO₂Me108 H Me Me H C(Me)₂CH₂SMe 109 H Me Me H C(Me)₂CH₂S(═O)Me 110 H Me Me HC(Me)₂CH₂SO₂Me 111 H Me Me H CH₂C(═O)NHMe 112 H Me Me H CH₂C(═O)N(Me)₂113 H Me Me H CH₂C(═O)NHEt 114 H Me Me H CH₂C(═O)NH-c-Pr 115 H Me Me HCH₂C(═O)NHCH₂CF₃ 116 H H Me Me CH₂Ph 117 H H Me Me CH₂-2-Py 118 H H MeMe CH₂-3-Py 119 H H Me Me CH₂CH₂OH 120 H H Me Me CH(CH₃)CH₂OH 121 H H MeMe C(CH₃)₂CH₂OH 122 H H Me Me CH₂CH₂OMe 123 H H Me Me CH(CH₃)CH₂OMe 124H H Me Me C(CH₃)₂CH₂OMe 125 H H Me Me CH₂CH₂SMe 126 H H Me MeCH₂CH₂S(═O)Me 127 H H Me Me CH₂CH₂SO₂Me 128 H H Me Me CH(Me)CH₂SMe 129 HH Me Me CHMeCH₂S(═O)Me 130 H H Me Me CH(Me)CH₂SO₂Me 131 H H Me MeC(Me)₂CH₂SMe 132 H H Me Me C(Me)₂CH₂S(═O)Me 133 H H Me Me C(Me)₂CH₂SO₂Me134 H H Me Me CH₂C(═O)NHMe 135 H H Me Me CH₂C(═O)N(Me)₂ 136 H H Me MeCH₂C(═O)NHEt 137 H H Me Me CH₂C(═O)NH-c-Pr 138 H H Me MeCH₂C(═O)NHCH₂CF₃ A is:

TABLE 49 Cmpd. Cmpd. Cmpd. Cmpd. Cmpd. Cmpd. Cmpd. Cmpd. Cmpd. Cmpd.Cmpd. 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 1-11 1-12 1-13 1-14 1-151-16 1-17 1-18 1-19 1-20 1-21 1-22 1-23 1-24 1-25 1-26 1-27 1-28 1-291-30 1-31 1-32 1-33 1-34 1-35 1-36 1-37 1-38 1-39 1-40 1-41 1-42 1-431-44 1-45 1-46 1-47 1-48 1-49 1-50 1-51 1-52 1-53 1-54 1-55 1-56 1-571-58 1-59 1-60 1-61 1-62 1-63 1-64 1-65 1-66 1-67 1-68 1-69 1-70 1-711-72 1-73 1-74 1-75 1-76 1-77 1-78 1-79 1-80 1-81 1-82 1-83 1-84 1-851-86 1-87 1-88 1-89 1-90 1-91 1-92 1-93 1-94 1-95 1-96 1-97 1-98 1-991-100 1-101 1-102 1-103 1-104 1-105 1-106 1-107 1-108 1-109 1-110 1-1111-112 1-113 1-114 1-115 1-116 1-117 1-118 1-119 1-120 1-121 1-122 1-1231-124 1-125 1-126 1-127 1-128 1-129 1-130 1-131 1-132 1-133 1-134 1-1351-136 1-137 1-138 1-139 1-140 1-141 1-142 1-143 1-144 1-145 1-146 1-1471-148 1-149 1-150 1-151 1-152 1-153 1-154 1-155 1-156 1-157 1-158 1-1591-160 1-161 1-162 1-163 1-164 1-165 1-166 1-167 1-168 1-169 1-170 1-1711-172 1-173 1-174 1-175 1-176 1-177 1-178 1-179 1-180 1-181 1-182 1-1831-184 2-93 2-94 2-95 2-96 2-97 2-98 2-99 2-100 2-101 2-102 2-103 2-1042-105 2-106 2-107 3-93 3-94 3-95 3-96 3-97 3-98 3-99 3-100 3-101 3-1023-103 3-104 3-105 3-106 3-107 4-93 4-94 4-95 4-96 4-97 4-98 4-99 4-1004-101 4-102 4-103 4-104 4-105 4-106 4-107 4-108 4-109 5-1 5-2 5-3 5-45-5 5-6 5-7 5-8 5-9 5-10 5-11 5-12 5-13 5-14 5-15 5-16 5-17 5-18 5-195-20 5-21 5-22 5-23 5-24 5-25 5-26 5-27 5-28 5-29 5-30 5-31 5-32 5-335-34 5-35 5-36 5-37 5-38 5-39 5-40 5-41 5-42 5-43 5-44 5-45 5-46 5-475-48 5-49 5-50 5-51 5-52 5-53 5-54 5-55 5-56 5-57 5-58 5-59 5-60 5-615-62 5-63 5-64 5-65 5-66 5-67 5-68 5-69 5-70 5-71 5-72 5-73 5-74 5-755-76 5-77 5-78 5-79 5-80 5-81 5-82 5-83 5-84 5-85 5-86 5-87 5-88 5-895-90 5-91 5-92 5-93 5-94 5-95 5-96 5-97 5-98 5-99 5-100 5-101 5-1025-103 5-104 5-105 5-106 5-107 5-108 5-109 5-110 5-111 5-112 5-113 5-1145-115 5-116 5-117 5-118 5-119 5-120 5-121 5-122 5-123 5-124 5-125 5-1265-127 5-128 5-129 5-130 5-131 5-132 5-133 5-134 5-135 5-136 5-137 5-1385-139 5-140 5-141 5-142 5-143 5-144 5-145 5-146 5-147 5-148 5-149 5-1505-151 5-152 5-153 5-154 5-155 5-156 5-157 5-158 5-159 5-160 5-161 5-1625-163 5-164 5-165 5-166 5-167 5-168 5-169 5-170 5-171 5-172 5-173 5-1745-175 5-176 5-177 5-178 5-179 5-180 5-181 5-182 5-183 5-184 6-93 6-946-95 6-96 6-97 6-98 6-99 6-100 6-101 6-102 6-103 6-104 6-105 6-106 6-1077-93 7-94 7-95 7-96 7-97 7-98 7-99 7-100 7-101 7-102 7-103 7-104 7-1057-106 7-107 8-93 8-94 8-95 8-96 8-97 8-98 8-99 8-100 8-101 8-102 8-1038-104 8-105 8-106 8-107 8-108 8-109 9-1 9-2 9-3 9-4 9-5 9-6 9-7 9-8 9-99-10 9-11 9-12 9-13 9-14 9-15 9-16 9-17 9-18 9-19 9-20 9-21 9-22 9-239-24 9-25 9-26 9-27 9-28 9-29 9-30 9-31 9-32 9-33 9-34 9-35 9-36 9-379-38 9-39 9-40 9-41 9-42 9-43 9-44 9-45 9-46 9-47 9-48 9-49 9-50 9-519-52 9-53 9-54 9-55 9-56 9-57 9-58 9-59 9-60 10-1 10-2 10-3 10-4 10-510-6 10-7 10-8 10-9 10-10 11-1 11-2 11-3 11-4 11-5 11-6 11-7 11-8 11-911-10 12-1 12-2 12-3 12-4 12-5 12-6 12-7 12-8 12-9 12-10 13-1 13-2 13-313-4 13-5 13-6 13-7 13-8 13-9 13-10 14-1 14-2 14-3 14-4 14-5 14-6 14-714-8 14-9 14-10 15-1 15-2 15-3 15-4 15-5 15-6 15-7 15-8 15-9 15-10 16-116-2 16-3 16-4 16-5 16-6 16-7 16-8 16-9 16-10 16-11 16-12 17-1 17-2 17-317-4 17-5 17-6 17-7 17-8 17-9 17-10 17-11 17-12 17-13 17-14 17-15 17-1617-17 17-18 17-19 17-20 17-21 17-22 17-23 17-24 17-25 17-26 17-27 17-2817-29 17-30 17-31 17-32 17-33 17-34 17-35 17-36 17-37 17-38 17-39 17-4017-41 17-42 17-43 17-44 17-45 17-46 17-47 17-48 17-49 17-50 17-51 17-5217-53 17-54 17-55 17-56 17-57 17-58 17-59 17-60 18-1 18-2 18-3 18-4 18-518-6 18-7 18-9 18-9 18-10 19-1 19-2 19-3 19-4 19-5 19-6 19-7 19-8 19-919-10 20-1 20-2 20-3 20-4 20-5 20-6 20-7 20-8 20-9 20-10 20-11 20-1220-13 20-14 20-15 20-16 20-17 20-18 20-19 21-1 21-2 21-3 21-4 21-5 21-621-7 21-8 21-9 21-10 21-11 21-12 21-13 21-14 21-15 21-16 21-17 21-1821-19 21-20 21-21 21-22 21-23 21-24 21-25 21-26 21-27 21-28 21-29 21-3021-31 21-32 21-33 21-34 21-35 21-36 21-37 21-38 21-39 21-40 21-41 21-4221-43 21-44 21-45 21-46 21-47 21-48 21-49 21-50 21-51 21-52 21-53 21-5421-55 21-56 21-57 21-58 21-59 21-60 22-1 22-2 22-3 22-4 22-5 22-6 22-722-9 22-9 22-10 23-1 23-2 23-3 23-4 23-5 23-6 23-7 23-8 23-9 23-10 24-124-2 24-3 24-4 24-5 24-6 24-7 24-8 24-9 24-10 24-11 24-12 24-13 24-1424-15 24-16 24-17 24-18 24-19 25-1 25-2 25-3 25-4 25-5 25-6 25-7 25-825-9 25-10 25-11 25-12 25-13 25-14 25-15 25-16 25-17 25-18 25-19 25-2025-21 25-22 25-23 25-24 25-25 25-26 25-27 25-28 25-29 25-30 25-31 25-3225-33 25-34 25-35 25-36 25-37 25-38 25-39 25-40 25-41 25-42 25-43 25-4425-45 25-46 25-47 25-48 25-49 25-50 25-51 25-52 25-53 25-54 25-55 25-5625-57 25-58 25-59 25-60 25-61 25-62 25-63 25-64 25-65 25-66 25-67 25-6825-69 25-70 25-71 25-72 25-73 25-74 25-75 25-76 25-77 25-78 25-79 25-8026-1 26-2 26-3 26-4 26-5 26-6 26-7 27-1 27-2 27-3 27-4 27-5 27-6 27-728-1 28-2 28-3 28-4 28-5 28-6 28-7 29-1 29-2 29-3 29-4 29-5 29-6 29-730-1 30-2 30-3 30-4 30-5 30-6 30-7 31-1 31-2 31-3 31-4 31-5 31-6 31-732-1 32-2 32-3 32-4 32-5 32-6 32-7 32-8 32-9 32-10 33-1 33-2 33-3 33-433-5 33-6 33-7 33-8 33-9 33-10 33-11 33-12 33-13 33-14 33-15 33-16 33-1733-18 33-19 33-20 33-21 33-22 33-23 33-24 33-25 33-26 33-27 33-28 33-2933-30 33-31 33-32 33-33 33-34 33-35 33-36 33-37 33-38 33-39 33-40 33-4133-42 33-43 33-44 33-45 33-46 33-47 33-48 33-49 33-50 33-51 33-52 33-5333-54 33-55 33-56 33-57 33-58 33-59 33-60 33-61 33-62 33-63 33-64 33-6533-66 33-67 33-68 33-69 33-70 34-11 34-12 34-13 34-14 34-15 34-16 34-1734-18 34-19 34-20 34-21 34-22 34-23 34-24 34-25 34-26 34-27 34-28 34-2934-30 34-46 34-47 34-48 34-49 34-50 34-51 34-52 34-53 34-54 34-55 35-1135-12 35-13 35-14 35-15 35-16 35-17 35-18 35-19 35-20 35-20 35-21 35-2235-23 35-24 35-25 35-26 35-27 35-28 35-29 35-30 35-46 35-47 35-48 35-4935-50 35-51 35-52 35-53 35-54 35-55 36-11 36-12 36-13 36-14 36-15 36-1636-17 36-18 36-19 36-20 36-22 36-23 36-24 36-25 36-26 36-27 36-28 36-2936-30 36-46 36-47 36-48 36-49 36-49 36-50 36-51 36-52 36-53 36-54 36-5537-11 37-12 37-13 37-14 37-14 37-15 37-16 37-17 37-18 37-19 37-20 37-2237-23 37-24 37-25 37-26 37-27 37-28 37-29 37-30 37-46 37-47 37-48 37-4937-50 37-51 37-52 37-53 37-54 37-55 38-11 38-12 38-13 38-14 38-15 38-1638-17 38-18 38-19 38-20 38-21 38-22 38-23 38-24 38-25 38-26 38-27 38-2838-29 38-30 38-46 38-47 38-48 38-49 38-50 38-51 38-52 38-53 38-54 38-5539-11 39-12 39-13 39-14 39-15 39-16 39-17 39-18 39-19 39-20 39-20 39-2139-22 39-23 39-24 39-25 39-26 39-27 39-28 39-29 39-30 39-46 39-47 39-4839-49 39-50 39-51 39-52 39-53 39-54 39-55 40-11 40-12 40-13 40-14 40-1540-16 40-17 40-18 40-19 40-20 40-22 40-23 40-24 40-25 40-26 40-27 40-2840-29 40-30 40-46 40-47 40-48 40-49 40-50 40-51 40-52 40-53 40-54 40-5540-56 40-57 40-58 40-59 40-60 41-1 41-2 41-3 41-4 41-5 41-6 41-7 41-841-9 41-10 41-11 41-12 41-13 41-14 41-15 41-16 41-17 41-18 41-19 41-2041-21 41-22 41-23 41-24 41-25 41-26 41-27 41-28 41-29 41-30 41-31 41-3241-33 41-34 41-35 41-36 41-37 41-38 41-39 41-40 41-41 41-42 41-43 41-4441-45 41-46 41-47 41-48 41-49 41-50 41-51 41-52 41-53 41-54 41-55 41-5641-57 41-58 41-59 41-60 41-61 41-62 41-63 41-64 41-65 41-66 41-67 41-6841-69 41-70 41-71 41-72 41-73 41-74 41-75 41-76 41-77 41-78 41-79 41-8041-81 41-82 41-83 41-84 41-85 41-86 41-87 41-88 41-89 41-90 41-91 41-9241-93 41-94 41-95 41-96 41-97 41-98 41-99 41-100 41-101 41-102 41-10341-104 41-105 41-106 41-107 41-108 41-109 41-110 41-111 41-112 41-11341-114 41-115 41-116 41-117 41-118 41-119 41-120 41-121 41-122 41-12341-124 41-125 41-126 41-127 41-128 41-129 41-130 41-131 41-132 41-13341-134 41-135 41-136 41-137 41-138 42-1 42-2 42-3 42-4 42-5 42-6 42-742-8 42-9 42-10 42-11 42-12 42-13 42-14 42-15 42-16 42-17 42-18 42-1942-20 42-21 42-22 42-23 42-70 42-71 42-72 42-73 42-74 42-75 42-76 42-7742-78 42-79 42-80 42-81 42-82 42-83 42-84 42-85 42-86 42-87 42-88 42-8942-90 42-91 42-92 43-1 43-2 43-3 43-4 43-5 43-6 43-7 43-8 43-9 43-1043-11 43-12 43-13 43-14 43-15 43-16 43-17 43-18 43-19 43-20 43-21 43-2243-23 43-70 43-71 43-72 43-73 43-74 43-75 43-76 43-77 43-78 43-79 43-8043-81 43-82 43-83 43-84 43-85 43-86 43-87 43-88 43-89 43-90 43-91 43-9244-1 44-2 44-3 44-4 44-5 44-6 44-7 44-8 44-9 44-10 44-11 44-12 44-1344-14 44-15 44-16 44-17 44-18 44-19 44-20 44-21 44-22 44-23 44-70 44-7144-72 44-73 44-74 44-75 44-76 44-77 44-78 44-79 44-80 44-81 44-82 44-8344-84 44-85 44-86 44-87 44-88 44-89 44-90 44-91 44-92 45-1 45-2 45-345-4 45-5 45-6 45-7 45-8 45-9 45-10 45-11 45-12 45-13 45-14 45-15 45-1645-17 45-18 45-19 45-20 45-21 45-22 45-23 45-70 45-71 45-72 45-73 45-7445-75 45-76 45-77 45-78 45-79 45-80 45-81 45-82 45-83 45-84 45-85 45-8645-87 45-88 45-89 45-90 45-91 45-92 46-1 46-2 46-3 46-4 46-5 46-6 46-746-8 46-9 46-10 46-11 46-12 46-13 46-14 46-15 46-16 46-17 46-18 46-1946-20 46-21 46-22 46-23 46-70 46-71 46-72 46-73 46-74 46-75 46-76 46-7746-78 46-79 46-80 46-81 46-82 46-83 46-84 46-85 46-86 46-87 46-88 46-8946-90 46-91 46-92 47-1 47-2 47-3 47-4 47-5 47-6 47-7 47-8 47-9 47-1047-11 47-12 47-13 47-14 47-15 47-16 47-17 47-18 47-19 47-20 47-21 47-2247-23 47-70 47-71 47-72 47-73 47-74 47-75 47-76 47-77 47-78 47-79 47-8047-81 47-82 47-83 47-84 47-85 47-86 47-87 47-88 47-89 47-90 47-91 47-9248-1 48-2 48-3 48-4 48-5 48-6 48-7 48-8 48-9 48-10 48-11 48-12 48-1348-14 48-15 48-16 48-17 48-18 48-19 48-20 48-21 48-22 48-23 48-70 48-7148-72 48-73 48-74 48-75 48-76 48-77 48-78 48-79 48-80 48-81 48-82 48-8348-84 48-85 48-86 48-87 48-88 48-89 48-90 48-91 48-92 48-93 48-94

TABLE 50

Cmpd. R² R¹⁶ R¹⁷ 1 3-Cl, 5-Cl Me Me 2 3-Cl, 5-Cl Et Me 3 3-Cl, 5-Cl n-PrMe 4 3-Cl, 5-Cl Et Et 5 3-Cl, 5-Cl i-Pr i-Pr 6 3-Br, 5-Br Me Me 7 3-Br,5-Br Et Me 8 3-Br, 5-Br n-Pr Me 9 3-Br, 5-Br Et Et 10 3-Br, 5-Br i-Pri-Pr 11 3-Cl, 4-Cl, 5-Cl Me Me 12 3-Cl, 4-Cl, 5-Cl Et Me 13 3-Cl, 4-Cl,5-Cl n-Pr Me 14 3-Cl, 4-Cl, 5-Cl Et Et 15 3-Cl, 4-Cl, 5-Cl i-Pr i-Pr 163-Cl, 4-F, 5-Cl Me Me 17 3-Cl, 4-F, 5-Cl Et Me 18 3-Cl, 4-F, 5-Cl n-PrMe 19 3-Cl, 4-F, 5-Cl Et Et 20 3-Cl, 4-F, 5-Cl i-Pr i-Pr 21 3-Cl Me Me22 3-Cl Et Me 23 3-Cl n-Pr Me 24 3-Cl Et Et 25 3-Cl i-Pr i-Pr 26 3-Br MeMe 27 3-Br Et Me 28 3-Br n-Pr Me 29 3-Br Et Et 30 3-Br i-Pr i-Pr 313-CF₃, 5-CF₃ Me Me 32 3-CF₃, 5-CF₃ Me Me 33 3-CF₃, 5-CF₃ n-Pr Me 343-CF₃, 5-CF₃ Et Et 35 3-CF₃, 5-CF₃ i-Pr i-Pr 36 3-CF₃, 5-Cl Me Me 373-CF₃, 5-Cl Et Me 38 3-CF₃, 5-Cl n-Pr Me 39 3-CF₃, 5-Cl Et Et 40 3-CF₃,5-Cl i-Pr i-Pr 41 3-CF₃, 5-Br Me Me 42 3-CF₃, 5-Br Et Me 43 3-CF₃, 5-Brn-Pr Me 44 3-CF₃, 5-Br Et Et 45 3-CF₃, 5-Br i-Pr i-Pr 46 3-Cl, 4-CN,5-Cl Me Me 47 3-Cl, 4-CN, 5-Cl Et Me 48 3-Cl, 4-CN, 5-Cl n-Pr Me 493-Cl, 4-CN, 5-Cl Et Et 50 3-Cl, 4-CN, 5-Cl i-Pr i-Pr 51 3-Cl, 4-Me, 5-ClMe Me 52 3-Cl, 4-Me, 5-Cl Et Me 53 3-Cl, 4-Me, 5-Cl n-Pr Me 54 3-Cl,4-Me, 5-Cl Et Et 55 3-Cl, 4-Me, 5-Cl i-Pr i-Pr 56 3-CF₃ Me H 57 3-CF₃ MeC(═O)CF₃ 58 3-CF₃ Me CN 59 3-CF₃ Et H 60 3-CF₃ Et C(═O)CF₃

TABLE 51

Cmpd. R² R¹⁹ R²⁰ 1 3-Cl, 5-Cl Me H 2 3-Cl, 5-Cl Me C(═O)CF₃ 3 3-Cl, 5-ClMe CN 4 3-Cl, 5-Cl Et H 5 3-Cl, 5-Cl Et C(═O)CF₃ 6 3-Br, 5-Br Me H 73-Br, 5-Br Me C(═O)CF₃ 8 3-Br, 5-Br Me CN 9 3-Br, 5-Br Et H 10 3-Br,5-Br Et C(═O)CF₃ 11 3-Cl, 4-Cl, 5-Cl Me H 12 3-Cl, 4-Cl, 5-Cl MeC(═O)CF₃ 13 3-Cl, 4-Cl, 5-Cl Me CN 14 3-Cl, 4-Cl, 5-Cl Et H 15 3-Cl,4-Cl, 5-Cl Et C(═O)CF₃ 16 3-Cl, 4-F, 5-Cl Me H 17 3-Cl, 4-F, 5-Cl MeC(═O)CF₃ 18 3-Cl, 4-F, 5-Cl Me CN 19 3-Cl, 4-F, 5-Cl Et H 20 3-Cl, 4-F,5-Cl Et C(═O)CF₃ 21 3-Cl Me H 22 3-Cl Me C(═O)CF₃ 23 3-Cl Me CN 24 3-ClEt H 25 3-Cl Et C(═O)CF₃ 26 3-Br Me H 27 3-Br Me C(═O)CF₃ 28 3-Br Me CN29 3-Br Et H 30 3-Br Et C(═O)CF₃ 31 3-CF₃, 5-CF₃ Me H 32 3-CF₃, 5-CF₃ MeC(═O)CF₃ 33 3-CF₃, 5-CF₃ Me CN 34 3-CF₃, 5-CF₃ Et H 35 3-CF₃, 5-CF₃ EtC(═O)CF₃ 36 3-CF₃, 5-Cl Me C(O)CF₃ 37 3-CF₃, 5-Cl Me CN 38 3-CF₃, 5-ClMe H 39 3-CF₃, 5-Cl Et C(O)CF₃ 40 3-CF₃, 5-Cl Et i-Pr 41 3-CF₃, 5-Br MeH 42 3-CF₃, 5-Br Me C(═O)CF₃ 43 3-CF₃, 5-Br Me CN 44 3-CF₃, 5-Br Et H 453-CF₃, 5-Br Et C(═O)CF₃ 46 3-Cl, 4-CN, 5-Cl Me H 47 3-Cl, 4-CN, 5-Cl MeC(═O)CF₃ 48 3-Cl, 4-CN, 5-Cl Me CN 49 3-Cl, 4-CN, 5-Cl Et H 50 3-Cl,4-CN, 5-Cl Et C(═O)CF₃ 51 3-Cl, 4-Me, 5-Cl Me H 52 3-Cl, 4-Me, 5-Cl MeC(═O)CF₃ 53 3-Cl, 4-Me, 5-Cl Me CN 54 3-Cl, 4-Me, 5-Cl Et H 55 3-Cl,4-Me, 5-Cl Et C(═O)CF₃ 56 3-CF₃ Me H 57 3-CF₃ Me C(═O)CF₃ 58 3-CF₃ Me CN59 3-CF₃ Et H 60 3-CF₃ Et C(O)CF₃

TABLE 52

Cmpd. R² R¹⁹ R²⁰ 1 3-Cl, 5-Cl Me H 2 3-Cl, 5-Cl Me C(═O)CF₃ 3 3-Cl, 5-ClMe CN 4 3-Cl, 5-Cl Et H 5 3-Cl, 5-Cl Et C(═O)CF₃ 6 3-Br, 5-Br Me H 73-Br, 5-Br Me C(═O)CF₃ 8 3-Br, 5-Br Me CN 9 3-Br, 5-Br Et H 10 3-Br,5-Br Et C(═O)CF₃ 11 3-Cl, 4-Cl, 5-Cl Me H 12 3-Cl, 4-Cl, 5-Cl MeC(═O)CF₃ 13 3-Cl, 4-Cl, 5-Cl Me CN 14 3-Cl, 4-Cl, 5-Cl Et H 15 3-Cl,4-Cl, 5-Cl Et C(═O)CF₃ 16 3-Cl, 4-F, 5-Cl Me H 17 3-Cl, 4-F, 5-Cl MeC(═O)CF₃ 18 3-Cl, 4-F, 5-Cl Me CN 19 3-Cl, 4-F, 5-Cl Et H 20 3-Cl, 4-F,5-Cl Et C(═O)CF₃ 21 3-Cl Me H 22 3-Cl Me C(═O)CF₃ 23 3-Cl Me CN 24 3-ClEt H 25 3-Cl Et C(═O)CF₃ 26 3-Br Me H 27 3-Br Me C(═O)CF₃ 28 3-Br Me CN29 3-Br Et H 30 3-Br Et C(═O)CF₃ 31 3-CF₃, 5-CF₃ Me H 32 3-CF₃, 5-CF₃ MeC(═O)CF₃ 33 3-CF₃, 5-CF₃ Me CN 34 3-CF₃, 5-CF₃ Et H 35 3-CF₃, 5-CF₃ EtC(═O)CF₃ 36 3-CF₃, 5-Cl Me C(O)CF₃ 37 3-CF₃, 5-Cl Me CN 38 3-CF₃, 5-ClMe H 39 3-CF₃, 5-Cl Et C(O)CF₃ 40 3-CF₃, 5-Cl Et i-Pr 41 3-CF₃, 5-Br MeH 42 3-CF₃, 5-Br Me C(═O)CF₃ 43 3-CF₃, 5-Br Me CN 44 3-CF₃, 5-Br Et H 453-CF₃, 5-Br Et C(═O)CF₃ 46 3-Cl, 4-CN, 5-Cl Me H 47 3-Cl, 4-CN, 5-Cl MeC(═O)CF₃ 48 3-Cl, 4-CN, 5-Cl Me CN 49 3-Cl, 4-CN, 5-Cl Et H 50 3-Cl,4-CN, 5-Cl Et C(═O)CF₃ 51 3-Cl, 4-Me, 5-Cl Me H 52 3-Cl, 4-Me, 5-Cl MeC(═O)CF₃ 53 3-Cl, 4-Me, 5-Cl Me CN 54 3-Cl, 4-Me, 5-Cl Et H 55 3-Cl,4-Me, 5-Cl Et C(═O)CF₃ 56 3-CF₃ Me H 57 3-CF₃ Me C(═O)CF₃ 58 3-CF₃ Me CN59 3-CF₃ Et H 60 3-CF₃ Et C(O)CF₃Formulation/Utility

A compound of this invention will generally be used as an invertebratepest control active ingredient in a composition, i.e. formulation, withat least one additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents, which serves as acarrier. The formulation or composition ingredients are selected to beconsistent with the physical properties of the active ingredient, modeof application and environmental factors such as soil type, moisture andtemperature.

Useful formulations include both liquid and solid compositions. Liquidcompositions include solutions (including emulsifiable concentrates),suspensions, emulsions (including microemulsions and/or suspoemulsions)and the like, which optionally can be thickened into gels. The generaltypes of aqueous liquid compositions are soluble concentrate, suspensionconcentrate, capsule suspension, concentrated emulsion, microemulsionand suspo-emulsion. The general types of nonaqueous liquid compositionsare emulsifiable concentrate, microemulsifiable concentrate, dispersibleconcentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules,pellets, prills, pastilles, tablets, filled films (including seedcoatings) and the like, which can be water-dispersible (“wettable”) orwater-soluble. Films and coatings formed from film-forming solutions orflowable suspensions are particularly useful for seed treatment. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. An emulsifiablegranule combines the advantages of both an emulsifiable concentrateformulation and a dry granular formulation. High-strength compositionsare primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable mediumbefore spraying. Such liquid and solid formulations are formulated to bereadily diluted in the spray medium, usually water. Spray volumes canrange from about from about one to several thousand liters per hectare,but more typically are in the range from about ten to several hundredliters per hectare. Sprayable formulations can be tank mixed with wateror another suitable medium for foliar treatment by aerial or groundapplication, or for application to the growing medium of the plant.Liquid and dry formulations can be metered directly into drip irrigationsystems or metered into the furrow during planting. Liquid and solidformulations can be applied onto seeds of crops and other desirablevegetation as seed treatments before planting to protect developingroots and other subterranean plant parts and/or foliage through systemicuptake.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand Water- 0.001-90  0-99.999 0-15 soluble Granules, Tablets and PowdersOil Dispersions, Suspensions,    1-50 40-99 0-50 Emulsions, Solutions(including Emulsifiable Concentrates) Dusts    1-25 70-99 0-5 Granulesand Pellets 0.001-99  5-99.999 0-15 High Strength Compositions   90-99 0-10 0-2

Solid diluents include, for example, clays such as bentonite,montmorillonite, attapulgite and kaolin, gypsum, cellulose, titaniumdioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose),silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. Typical solid diluentsare described in Watkins et al., Handbook of Insecticide Dust Diluentsand Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides(e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide,N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol,triethylene glycol, propylene glycol, dipropylene glycol, polypropyleneglycol, propylene carbonate, butylene carbonate, paraffins (e.g., whitemineral oils, normal paraffins, isoparaffins), alkylbenzenes,alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, triacetin,aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes,alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone,isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamylacetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate,tridecyl acetate and isobornyl acetate, other esters such as alkylatedlactate esters, dibasic esters and γ-butyrolactone, and alcohols, whichcan be linear, branched, saturated or unsaturated, such as methanol,ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol,n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol,isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleylalcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol andbenzyl alcohol. Liquid diluents also include glycerol esters ofsaturated and unsaturated fatty acids (typically C₆-C₂₂), such as plantseed and fruit oils (e.g, oils of olive, castor, linseed, sesame, corn(maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean,rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beeftallow, pork tallow, lard, cod liver oil, fish oil), and mixturesthereof. Liquid diluents also include alkylated fatty acids (e.g.,methylated, ethylated, butylated) wherein the fatty acids may beobtained by hydrolysis of glycerol esters from plant and animal sources,and can be purified by distillation. Typical liquid diluents aredescribed in Marsden, Solvents Guide, 2nd Ed., Interscience, New York,1950.

The solid and liquid compositions of the present invention often includeone or more surfactants. When added to a liquid, surfactants (also knownas “surface-active agents”) generally modify, most often reduce, thesurface tension of the liquid. Depending on the nature of thehydrophilic and lipophilic groups in a surfactant molecule, surfactantscan be useful as wetting agents, dispersants, emulsifiers or defoamingagents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionicsurfactants useful for the present compositions include, but are notlimited to: alcohol alkoxylates such as alcohol alkoxylates based onnatural and synthetic alcohols (which may be branched or linear) andprepared from the alcohols and ethylene oxide, propylene oxide, butyleneoxide or mixtures thereof; amine ethoxylates, alkanolamides andethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylatedsoybean, castor and rapeseed oils; alkylphenol alkoxylates such asoctylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenolethoxylates and dodecyl phenol ethoxylates (prepared from the phenolsand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); block polymers prepared from ethylene oxide or propylene oxideand reverse block polymers where the terminal blocks are prepared frompropylene oxide; ethoxylated fatty acids; ethoxylated fatty esters andoils; ethoxylated methyl esters; ethoxylated tristyrylphenol (includingthose prepared from ethylene oxide, propylene oxide, butylene oxide ormixtures thereof); fatty acid esters, glycerol esters, lanolin-basedderivatives, polyethoxylate esters such as polyethoxylated sorbitanfatty acid esters, polyethoxylated sorbitol fatty acid esters andpolyethoxylated glycerol fatty acid esters; other sorbitan derivativessuch as sorbitan esters; polymeric surfactants such as randomcopolymers, block copolymers, alkyd peg (polyethylene glycol) resins,graft or comb polymers and star polymers; polyethylene glycols (pegs);polyethylene glycol fatty acid esters; silicone-based surfactants; andsugar-derivatives such as sucrose esters, alkyl polyglycosides and alkylpolysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenolethoxylates; diphenyl sulfonate derivatives; lignin and ligninderivatives such as lignosulfonates; maleic or succinic acids or theiranhydrides; olefin sulfonates; phosphate esters such as phosphate estersof alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates andphosphate esters of styryl phenol ethoxylates; protein-basedsurfactants; sarcosine derivatives; styryl phenol ether sulfate;sulfates and sulfonates of oils and fatty acids; sulfates and sulfonatesof ethoxylated alkylphenols; sulfates of alcohols; sulfates ofethoxylated alcohols; sulfonates of amines and amides such asN,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, anddodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes;sulfonates of naphthalene and alkyl naphthalene; sulfonates offractionated petroleum; sulfosuccinamates; and sulfosuccinates and theirderivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides andethoxylated amides; amines such as N-alkyl propanediamines,tripropylenetriamines and dipropylenetetramines, and ethoxylated amines,ethoxylated diamines and propoxylated amines (prepared from the aminesand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); amine salts such as amine acetates and diamine salts;quaternary ammonium salts such as quaternary salts, ethoxylatedquaternary salts and diquaternary salts; and amine oxides such asalkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic andanionic surfactants or mixtures of nonionic and cationic surfactants.Nonionic, anionic and cationic surfactants and their recommended usesare disclosed in a variety of published references includingMcCutcheon's Emulsifiers and Detergents, annual American andInternational Editions published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopediaof Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; andA. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition,John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliariesand additives, known to those skilled in the art as formulation aids(some of which may be considered to also function as solid diluents,liquid diluents or surfactants). Such formulation auxiliaries andadditives may control: pH (buffers), foaming during processing(antifoams such polyorganosiloxanes), sedimentation of activeingredients (suspending agents), viscosity (thixotropic thickeners),in-container microbial growth (antimicrobials), product freezing(antifreezes), color (dyes/pigment dispersions), wash-off (film formersor stickers), evaporation (evaporation retardants), and otherformulation attributes. Film formers include, for example, polyvinylacetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinylacetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers andwaxes. Examples of formulation auxiliaries and additives include thoselisted in McCutcheon's Volume 2: Functional Materials, annualInternational and North American editions published by McCutcheon'sDivision, The Manufacturing Confectioner Publishing Co.; and PCTPublication WO 03/024222.

The compound of Formula 1 and any other active ingredients are typicallyincorporated into the present compositions by dissolving the activeingredient in a solvent or by grinding in a liquid or dry diluent.Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. If the solvent of a liquid compositionintended for use as an emulsifiable concentrate is water-immiscible, anemulsifier is typically added to emulsify the active-containing solventupon dilution with water. Active ingredient slurries, with particlediameters of up to 2,000 μm can be wet milled using media mills toobtain particles with average diameters below 3 μm. Aqueous slurries canbe made into finished suspension concentrates (see, for example, U.S.Pat. No. 3,060,084) or further processed by spray drying to formwater-dispersible granules. Dry formulations usually require dry millingprocesses, which produce average particle diameters in the 2 to 10 μmrange. Dusts and powders can be prepared by blending and usuallygrinding (such as with a hammer mill or fluid-energy mill). Granules andpellets can be prepared by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See Browning,“Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963,pages 8-57 and following, and WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. No.4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can beprepared as taught in U.S. Pat. Nos. 5,180,587, 5,232,701 and 5,208,030.Films can be prepared as taught in GB 2,095,558 and U.S. Pat. No.3,299,566.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989; and Developmentsin formulation technology, PJB Publications, Richmond, UK, 2000.

In the following Examples, all percentages are by weight and allformulations are prepared in conventional ways. Compound numbers referto compounds in Index Tables A-G. Without further elaboration, it isbelieved that one skilled in the art using the preceding description canutilize the present invention to its fullest extent. The followingExamples are, therefore, to be constructed as merely illustrative, andnot limiting of the disclosure in any way whatsoever. Percentages are byweight except where otherwise indicated.

EXAMPLE A

High Strength Concentrate Compound 4 98.5% silica aerogel 0.5% syntheticamorphous fine silica 1.0%

EXAMPLE B

Wettable Powder Compound 44 65.0% dodecylphenol polyethylene glycolether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0%montmorillonite (calcined) 23.0%

EXAMPLE C

Granule Compound 47 10.0% attapulgite granules (low volatile matter,90.0% 0.71/0.30 mm; U.S.S. No. 25-50 sieves)

EXAMPLE D

Extruded Pellet Compound 49 25.0% anhydrous sodium sulfate 10.0% crudecalcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0%calcium/magnesium bentonite 59.0%

EXAMPLE E

Emulsifiable Concentrate Compound 50 10.0% polyoxyethylene sorbitolhexoleate 20.0% C₆-C₁₀ fatty acid methyl ester 70.0%

EXAMPLE F

Microemulsion Compound 45 5.0% polyvinylpyrrolidone-vinyl acetatecopolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water20.0%

EXAMPLE G

Seed Treatment Compound 66 20.00% polyvinylpyrrolidone-vinyl acetatecopolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00%polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol(POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water65.75%

EXAMPLE H

Fertilizer Stick Compound 76 2.50% pyrrolidone-styrene copolymer 4.80%tristyrylphenyl 16-ethoxylate 2.30% talc 0.80% corn starch 5.00%Nitrophoska ® Permanent 15-9-15 36.00% slow-release fertilizer (BASF)kaolin 38.00% water 10.60%

Compounds of this invention exhibit activity against a wide spectrum ofinvertebrate pests. These pests include invertebrates inhabiting avariety of environments such as, for example, plant foliage, roots,soil, harvested crops or other foodstuffs, building structures or animalinteguments. These pests include, for example, invertebrates feeding onfoliage (including leaves, stems, flowers and fruits), seeds, wood,textile fibers or animal blood or tissues, and thereby causing injury ordamage to, for example, growing or stored agronomic crops, forests,greenhouse crops, ornamentals, nursery crops, stored foodstuffs or fiberproducts, or houses or other structures or their contents, or beingharmful to animal health or public health. Those skilled in the art willappreciate that not all compounds are equally effective against allgrowth stages of all pests.

These present compounds and compositions are thus useful agronomicallyfor protecting field crops from phytophagous invertebrate pests, andalso nonagronomically for protecting other horticultural crops andplants from phytophagous invertebrate pests. This utility includesprotecting crops and other plants (i.e. both agronomic and nonagronomic)that contain genetic material introduced by genetic engineering (i.e.transgenic) or modified by mutagenesis to provide advantageous traits.Examples of such traits include tolerance to herbicides, resistance tophytophagous pests (e.g., insects, mites, aphids, spiders, nematodes,snails, plant-pathogenic fungi, bacteria and viruses), improved plantgrowth, increased tolerance of adverse growing conditions such as highor low temperatures, low or high soil moisture, and high salinity,increased flowering or fruiting, greater harvest yields, more rapidmaturation, higher quality and/or nutritional value of the harvestedproduct, or improved storage or process properties of the harvestedproducts. Transgenic plants can be modified to express multiple traits.Examples of plants containing traits provided by genetic engineering ormutagenesis include varieties of corn, cotton, soybean and potatoexpressing an insecticidal Bacillus thuringiensis toxin such as YIELDGARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN® and NEWLEAF®, andherbicide-tolerant varieties of corn, cotton, soybean and rapeseed suchas ROUNDUP READY®, LIBERTY LINK®, IMI®, STS® and CLEARFIELD®, as well ascrops expressing N-acetyltransferase (GAT) to provide resistance toglyphosate herbicide, or crops containing the HRA gene providingresistance to herbicides inhibiting acetolactate synthase (ALS). Thepresent compounds and compositions may interact synergistically withtraits introduced by genetic engineering or modified by mutagenesis,thus enhancing phenotypic expression or effectiveness of the traits orincreasing the invertebrate pest control effectiveness of the presentcompounds and compositions. In particular, the present compounds andcompositions may interact synergistically with the phenotypic expressionof proteins or other natural products toxic to invertebrate pests toprovide greater-than-additive control of these pests.

Compositions of this invention can also optionally comprise plantnutrients, e.g., a fertilizer composition comprising at least one plantnutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium,magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of noteare compositions comprising at least one fertilizer compositioncomprising at least one plant nutrient selected from nitrogen,phosphorus, potassium, sulfur, calcium and magnesium. Compositions ofthe present invention which further comprise at least one plant nutrientcan be in the form of liquids or solids. Of note are solid formulationsin the form of granules, small sticks or tablets. Solid formulationscomprising a fertilizer composition can be prepared by mixing thecompound or composition of the present invention with the fertilizercomposition together with formulating ingredients and then preparing theformulation by methods such as granulation or extrusion. Alternativelysolid formulations can be prepared by spraying a solution or suspensionof a compound or composition of the present invention in a volatilesolvent onto a previous prepared fertilizer composition in the form ofdimensionally stable mixtures, e.g., granules, small sticks or tablets,and then evaporating the solvent.

Examples of agronomic or nonagronomic invertebrate pests include eggs,larvae and adults of the order Lepidoptera, such as armyworms, cutworms,loopers, and heliothines in the family Noctuidae (e.g., pink stem borer(Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioidesLefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm(Spodoptera fugiperda J. E. Smith), beet armyworm (Spodoptera exiguaHübner), cotton leafworm (Spodoptera littoralis Boisduval),yellowstriped armyworm (Spodoptera ornithogalli Guenée), black cutworm(Agrotis ipsilon Hufnagel), velvetbean caterpillar (Anticarsiagemmatalis Hübner), green fruitworm (Lithophane antennata Walker),cabbage armyworm (Barathra brassicae Linnaeus), soybean looper(Pseudoplusia includens Walker), cabbage looper (Trichoplusia niHübner), tobacco budworm (Heliothis virescens Fabricius)); borers,casebearers, webworms, coneworms, cabbageworms and skeletonizers fromthe family Pyralidae (e.g., European corn borer (Ostrinia nubilalisHübner), navel orangeworm (Amyelois transitella Walker), corn rootwebworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae:Crambinae) such as sod worm (Herpetogramma licarsisalis Walker),sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer(Neoleucinodes elegantalis Guenée), green leafroller (Cnaphalocerusmedinalis), grape leaffolder (Desmia funeralis Hübner), melon worm(Diaphania nitidalis Stoll), cabbage center grub (Helluala hydralisGuenée), yellow stem borer (Scirpophaga incertulas Walker), early shootborer (Scirpophaga infuscatellus Snellen), white stem borer (Scirpophagainnotata Walker), top shoot borer (Scirpophaga nivella Fabricius),dark-headed rice borer (Chilo polychrysus Meyrick), cabbage clustercaterpillar (Crocidolomia binotalis English)); leafrollers, budworms,seed worms, and fruit worms in the family Tortricidae (e.g., codlingmoth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteanaClemens), oriental fruit moth (Grapholita molesta Busck), citrus falsecodling moth (Cryptophlebia leucotreta Meyrick), citrus borer(Ecdytolopha aurantiana Lima), redbanded leafroller (Argyrotaeniavelutinana Walker), obliquebanded leafroller (Choristoneura rosaceanaHarris), light brown apple moth (Epiphyas postvittana Walker), Europeangrape berry moth (Eupoecilia ambiguella Hübner), apple bud moth(Pandemis pyrusana Kearfott), omnivorous leafroller (Platynota stultanaWalsingham), barred fruit-tree tortrix (Pandemis cerasana Hübner), applebrown tortrix (Pandemis heparana Denis & Schiffermüller)); and manyother economically important lepidoptera (e.g., diamondback moth(Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiellaSaunders), gypsy moth (Lymantria dispar Linnaeus), peach fruit borer(Carposina niponensis Walsingham), peach twig borer (Anarsia lineatellaZeller), potato tuberworm (Phthorimaea operculella Zeller), spottedteniform leafminer (Lithocolletis blancardella Fabricius), Asiatic appleleafminer (Lithocolletis ringoniella Matsumura), rice leaffolder(Lerodea eufala Edwards), apple leafminer (Leucoptera scitella Zeller));eggs, nymphs and adults of the order Blattodea including cockroachesfrom the families Blattellidae and Blattidae (e.g., oriental cockroach(Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinaiMizukubo), German cockroach (Blattella germanica Linnaeus), brownbandedcockroach (Supella longipalpa Fabricius), American cockroach(Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunneaBurmeister), Madeira cockroach (Leucophaea maderae Fabricius)), smokybrown cockroach (Periplaneta fuliginosa Service), Australian Cockroach(Periplaneta australasiae Fabr.), lobster cockroach (Nauphoeta cinereaOlivier) and smooth cockroach (Symploce pallens Stephens)); eggs, foliarfeeding, fruit feeding, root feeding, seed feeding and vesicular tissuefeeding larvae and adults of the order Coleoptera including weevils fromthe families Anthribidae, Bruchidae, and Curculionidae (e.g., bollweevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrusoryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus),rice weevil (Sitophilus oryzae Linnaeus)), annual bluegrass weevil(Listronotus maculicollis Dietz), bluegrass billbug (Sphenophorusparvulus Gyllenhal), hunting billbug (Sphenophorus venatus vestitus),Denver billbug (Sphenophorus cicatristriatus Fahraeus)); flea beetles,cucumber beetles, rootworms, leaf beetles, potato beetles, andleafminers in the family Chrysomelidae (e.g., Colorado potato beetle(Leptinotarsa decemlineata Say), western corn rootworm (Diabroticavirgifera virgifera LeConte)); chafers and other beetles from the familyScarabaeidae (e.g., Japanese beetle (Popillia japonica Newman), orientalbeetle (Anomala orientalis Waterhouse, Exomala orientalis (Waterhouse)Baraud), northern masked chafer (Cyclocephala borealis Arrow), southernmasked chafer (Cyclocephala immaculata Olivier or C. lurida Bland), dungbeetle and white grub (Aphodius spp.), black turfgrass ataenius(Ataenius spretulus Haldeman), green June beetle (Cotinis nitidaLinnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/Junebeetles (Phyllophaga spp.) and European chafer (Rhizotrogus majalisRazoumowsky)); carpet beetles from the family Dermestidae; wirewormsfrom the family Elateridae; bark beetles from the family Scolytidae andflour beetles from the family Tenebrionidae. In addition, agronomic andnonagronomic pests include: eggs, adults and larvae of the orderDermaptera including earwigs from the family Forficulidae (e.g.,European earwig (Forficula auricularia Linnaeus), black earwig(Chelisoches morio Fabricius)); eggs, immatures, adults and nymphs ofthe orders Hemiptera and Homoptera such as, plant bugs from the familyMiridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoascaspp.) from the family Cicadellidae, bed bugs (e.g., Cimex lectulariusLinnaeus) from the family Cimicidae, planthoppers from the familiesFulgoroidae and Delphacidae, treehoppers from the family Membracidae,psyllids from the family Psyllidae, whiteflies from the familyAleyrodidae, aphids from the family Aphididae, phylloxera from thefamily Phylloxeridae, mealybugs from the family Pseudococcidae, scalesfrom the families Coccidae, Diaspididae and Margarodidae, lace bugs fromthe family Tingidae, stink bugs from the family Pentatomidae, chinchbugs (e.g., hairy chinch bug (Blissus leucopterus hirtus Montandon) andsouthern chinch bug (Blissus insularis Barber)) and other seed bugs fromthe family Lygaeidae, spittlebugs from the family Cercopidae squash bugsfrom the family Coreidae, and red bugs and cotton stainers from thefamily Pyrrhocoridae. Also included are eggs, larvae, nymphs and adultsof the order Acari (mites) such as spider mites and red mites in thefamily Tetranychidae (e.g., European red mite (Panonychus ulmi Koch),two spotted spider mite (Tetranychus urticae Koch), McDaniel mite(Tetranychus mcdanieli McGregor)); flat mites in the familyTenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor));rust and bud mites in the family Eriophyidae and other foliar feedingmites and mites important in human and animal health, i.e. dust mites inthe family Epidermoptidae, follicle mites in the family Demodicidae,grain mites in the family Glycyphagidae; ticks in the family Ixodidae,commonly known as hard ticks (e.g., deer tick (Ixodes scapularis Say),Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick(Dermacentor variabilis Say), lone star tick (Amblyomma americanumLinnaeus)) and ticks in the family Argasidae, commonly known as softticks (e.g., relapsing fever tick (Ornithodoros turicata), common fowltick (Argas radiatus)); scab and itch mites in the families Psoroptidae,Pyemotidae, and Sarcoptidae; eggs, adults and immatures of the orderOrthoptera including grasshoppers, locusts and crickets (e.g., migratorygrasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialisThomas), American grasshoppers (e.g., Schistocerca americana Drury),desert locust (Schistocerca gregaria Forskal), migratory locust (Locustamigratoria Linnaeus), bush locust (Zonocerus spp.), house cricket(Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket(Scapteriscus vicinus Scudder) and southern mole cricket (Scapteriscusborellii Giglio-Tos)); eggs, adults and immatures of the order Dipteraincluding leafminers (e.g., Liriomyza spp. such as serpentine vegetableleafminer (Liriomyza sativae Blanchard)), midges, fruit flies(Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots,house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g.,Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g.,Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g.,Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies(e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.),cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.),keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes(e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g.,Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids,and other Nematocera; eggs, adults and immatures of the orderThysanoptera including onion thrips (Thrips tabaci Lindeman), flowerthrips (Frankliniella spp.), and other foliar feeding thrips; insectpests of the order Hymenoptera including ants of the Family Formicidaeincluding the Florida carpenter ant (Camponotus floridanus Buckley), redcarpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant(Camponotus pennsylvanicus De Geer), white-footed ant (Technomyrmexalbipes fr. Smith), big headed ants (Pheidole sp.), ghost ant (Tapinomamelanocephalum Fabricius); Pharaoh ant (Monomorium pharaonis Linnaeus),little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsisgeminata Fabricius), red imported fire ant (Solenopsis invicta Buren),Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechinalongicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus),cornfield ant (Lasius alienus Förster) and odorous house ant (Tapinomasessile Say). Other Hymenoptera including bees (including carpenterbees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.;Cephus spp.); insect pests of the order Isoptera including termites inthe Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur),Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g.,Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen)families, the eastern subterranean termite (Reticulitermes flavipesKollar), western subterranean termite (Reticulitermes hesperus Banks),Formosan subterranean termite (Coptotermes formosanus Shiraki), WestIndian drywood termite (Incisitermes immigrans Snyder), powder posttermite (Cryptotermes brevis Walker), drywood termite (Incisitermessnyderi Light), southeastern subterranean termite (Reticulitermesvirginicus Banks), western drywood termite (Incisitermes minor Hagen),arboreal termites such as Nasutitermes sp. and other termites ofeconomic importance; insect pests of the order Thysanura such assilverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobiadomestica Packard); insect pests of the order Mallophaga and includingthe head louse (Pediculus humanus capitis De Geer), body louse(Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineusNitszch), dog biting louse (Trichodectes canis De Geer), fluff louse(Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank),short-nosed cattle louse (Haematopinus eurysternus Nitzsch), long-nosedcattle louse (Linognathus vituli Linnaeus) and other sucking and chewingparasitic lice that attack man and animals; insect pests of the orderSiphonoptera including the oriental rat flea (Xenopsylla cheopisRothschild), cat flea (Ctenocephalides felis Bouche), dog flea(Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinaeSchrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea(Pulex irritans Linnaeus) and other fleas afflicting mammals and birds.Additional arthropod pests covered include: spiders in the order Araneaesuch as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik)and the black widow spider (Latrodectus mactans Fabricius), andcentipedes in the order Scutigeromorpha such as the house centipede(Scutigera coleoptrata Linnaeus). Compounds of the present inventionalso have activity on members of the Classes Nematoda, Cestoda,Trematoda, and Acanthocephala including economically important membersof the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida,and Enoplida such as but not limited to economically importantagricultural pests (i.e. root knot nematodes in the genus Meloidogyne,lesion nematodes in the genus Pratylenchus, stubby root nematodes in thegenus Trichodorus, etc.) and animal and human health pests (i.e. alleconomically important flukes, tapeworms, and roundworms, such asStrongylus vulgaris in horses, Toxocara canis in dogs, Haemonchuscontortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephalaperfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).

Compounds of the invention show particularly high activity against pestsin the order Lepidoptera (e.g., Alabama argillacea Hübner (cotton leafworm), Archips argyrospila Walker (fruit tree leaf roller), A. rosanaLinnaeus (European leaf roller) and other Archips species, Chilosuppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenée(rice leaf roller), Crambus caliginosellus Clemens (corn root webworm),Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonellaLinnaeus (codling moth), Earias insulana Boisduval (spiny bollworm),Earias vittella Fabricius (spotted bollworm), Helicoverpa armigeraHübner (American bollworm), Helicoverpa zea Boddie (corn earworm),Heliothis virescens Fabricius (tobacco budworm), Herpetogrammalicarsisalis Walker (sod webworm), Lobesia botrana Denis &Schiffermüller (grape berry moth), Pectinophora gossypiella Saunders(pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer),Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus(small white butterfly), Plutella xylostella Linnaeus (diamondbackmoth), Spodoptera exigua Hübner (beet armyworm), Spodoptera lituraFabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperdaJ. E. Smith (fall armyworm), Trichoplusia ni Hübner (cabbage looper) andTuta absoluta Meyrick (tomato leafminer)).

Compounds of the invention also have significant activity on membersfrom the order Homoptera including: Acyrthosiphon pisum Harris (peaaphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (blackbean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphispomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid),Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefoliiCockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko(Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy appleaphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopteruspruni Geoffroy (mealy plum aphid), Lipaphis erysimi Kaltenbach (turnipaphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosiphumeuphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potatoaphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid),Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch(corn leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid),Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius(English grain aphid), Therioaphis maculata Buckton (spotted alfalfaaphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid),and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp.(adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisiatabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisiaargentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citriAshmead (citrus whitefly) and Trialeurodes vaporariorum Westwood(greenhouse whitefly); Empoasca fabae Harris (potato leafhopper),Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestesquadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler(green leafhopper), Nephotettix nigropictus Stål (rice leafhopper),Nilaparvata lugens Stål (brown planthopper), Peregrinus maidis Ashmead(corn planthopper), Sogatella furcifera Horvath (white-backedplanthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocybapomaria McAtee white apple leafhopper, Erythroneoura spp. (grapeleafhoppers); Magicidada septendecim Linnaeus (periodical cicada);Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotusperniciosus Comstock (San Jose scale); Planococcus citri Risso (citrusmealybug); Pseudococcus spp. (other mealybug complex); Cacopsyllapyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmonpsylla).

Compounds of this invention also have activity on members from the orderHemiptera including: Acrosternum hilare Say (green stink bug), Anasatristis De Geer (squash bug), Blissus leucopterus leucopterus Say(chinch bug), Cimex lectularius Linnaeus (bed bug) Corythuca gossypiiFabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug),Dysdercus suturellus Herrich-Schäffer (cotton stainer), Euchistus servusSay (brown stink bug), Euchistus variolarius Palisot de Beauvois(one-spotted stink bug), Graptosthetus spp. (complex of seed bugs),Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolarisPalisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus(southern green stink bug), Oebalus pugnax Fabricius (rice stink bug),Oncopeltus fasciatus Dallas (large milkweed bug), Pseudatomoscelisseriatus Reuter (cotton fleahopper). Other insect orders controlled bycompounds of the invention include Thysanoptera (e.g., Frankliniellaoccidentalis Pergande (western flower thrips), Scirthothrips citriMoulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips),and Thrips tabaci Lindeman (onion thrips); and the order Coleoptera(e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachnavarivestis Mulsant (Mexican bean beetle) and wireworms of the generaAgriotes, Athous or Limonius).

Note that some contemporary classification systems place Homoptera as asuborder within the order Hemiptera.

Of note is use of compounds of this invention for controlling silverleafwhitefly (Bemisia argentifolii). Of note is use of compounds of thisinvention for controlling western flower thrip (Frankliniellaoccidentalis). Of note is use of compounds of this invention forcontrolling potato leafhopper (Empoasca fabae). Of note is use ofcompounds of this invention for controlling corn planthopper (Peregrinusmaidis). Of note is use of compounds of this invention for controllingcotton melon aphid (Aphis gossypii). Of note is use of compounds of thisinvention for controlling green peach aphid (Myzus persicae). Of note isuse of compounds of this invention for controlling diamondback moth(Plutella xylostella). Of note is use of compounds of this invention forcontrolling fall armyworm (Spodoptera frugiperda).

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including insecticides,fungicides, nematocides, bactericides, acaricides, herbicides, herbicidesafeners, growth regulators such as insect molting inhibitors androoting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, other biologically activecompounds or entomopathogenic bacteria, virus or fungi to form amulti-component pesticide giving an even broader spectrum of agronomicand nonagronomic utility. Thus the present invention also pertains to acomposition comprising a biologically effective amount of a compound ofFormula 1, an N-oxide or salt thereof, and an effective amount of atleast one additional biologically active compound or agent and canfurther comprise at least one of surfactants, solid diluents or liquiddiluents. For mixtures of the present invention, the other biologicallyactive compounds or agents can be formulated together with the presentcompounds, including the compounds of Formula 1, to form a premix, orthe other biologically active compounds or agents can be formulatedseparately from the present compounds, including the compounds ofFormula 1, and the two formulations combined together before application(e.g., in a spray tank) or, alternatively, applied in succession.

Examples of such biologically active compounds or agents with whichcompounds of this invention can be formulated are insecticides such asabamectin, acephate, acequinocyl, acetamiprid, acrinathrin, amidoflumet,amitraz, avermectin, azadirachtin, azinphos-methyl, bifenthrin,bifenazate, bistrifluoron, borate,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol,chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos,chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin,cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenothiocarb,fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid,flubendiamide, flucythrinate, flufenerim, flufenoxuron, fluvalinate,tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide,hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb,insecticidal soaps, isofenphos, lufenuron, malathion, metaflumizone,metaldehyde, methamidophos, methidathion, methiodicarb, methomyl,methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide,nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion,parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon,pirimicarb, profenofos, profluthrin, propargite, protrifenbute,pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,sulprofos, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin,terbufos, tetrachlorvinphos, tetramethrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon, triflumuron, Bacillus thuringiensis delta-endotoxins,entomopathogenic bacteria, entomopathogenic viruses and entomopathogenicfungi.

Of note are insecticides such as abamectin, acetamiprid, acrinathrin,amitraz, avermectin, azadirachtin, bifenthrin,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole,chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate,fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate,formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, metaflumizone, methiodicarb, methomyl,methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl,pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillusthuringiensis delta-endotoxins, all strains of Bacillus thuringiensisand all strains of Nucleo polyhydrosis viruses.

One embodiment of biological agents for mixing with compounds of thisinvention include entomopathogenic bacteria such as Bacillusthuringiensis, and the encapsulated delta-endotoxins of Bacillusthuringiensis (e.g., Cellcap, MPV, MPVII); entomopathogenic fungi suchas green muscardine fungus; and entomopathogenic (both naturallyoccurring and genetically modified) viruses including baculovirus,nucleopolyhedro virus (NPV) such as Helicoverpa zea nucleopolyhedrovirus(HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); andgranulosis virus (GV) such as Cydia pomonella granulosis virus (CpGV).

Of particular note is such a combination where the other invertebratepest control active ingredient belongs to a different chemical class orhas a different site of action than the compound of Formula 1. Incertain instances, a combination with at least one other invertebratepest control active ingredient having a similar spectrum of control buta different site of action will be particularly advantageous forresistance management. Thus, a composition of the present invention canfurther comprise at least one additional invertebrate pest controlactive ingredient having a similar spectrum of control but belonging toa different chemical class or having a different site of action. Theseadditional biologically active compounds or agents include, but are notlimited to, sodium channel modulators such as bifenthrin, cypermethrin,cyhalothrin, lambda-cyhalothrin, cyfluthrin, beta-cyfluthrin,deltamethrin, dimefluthrin, esfenvalerate, fenvalerate, indoxacarb,metofluthrin, profluthrin, pyrethrin and tralomethrin; cholinesteraseinhibitors such as chlorpyrifos, methomyl, oxamyl, thiodicarb andtriazamate; neonicotinoids such as acetamiprid, clothianidin,dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid andthiamethoxam; insecticidal macrocyclic lactones such as spinetoram,spinosad, abamectin, avermectin and emamectin; GABA (γ-aminobutyricacid)-gated chloride channel antagonists such as avermectin or blockerssuch as ethiprole and fipronil; chitin synthesis inhibitors such asbuprofezin, cyromazine, flufenoxuron, hexaflumuron, lufenuron,novaluron, noviflumuron and triflumuron; juvenile hormone mimics such asdiofenolan, fenoxycarb, methoprene and pyriproxyfen; octopamine receptorligands such as amitraz; molting inhibitors and ecdysone agonists suchas azadirachtin, methoxyfenozide and tebufenozide; ryanodine receptorligands such as ryanodine, anthranilic diamides such aschlorantraniliprole (see U.S. Pat. No. 6,747,047, PCT Publications WO2003/015518 and WO 2004/067528) and flubendiamide (see U.S. Pat. No.6,603,044); nereistoxin analogs such as cartap; mitochondrial electrontransport inhibitors such as chlorfenapyr, hydramethylnon and pyridaben;lipid biosynthesis inhibitors such as spirodiclofen and spiromesifen;cyclodiene insecticides such as dieldrin or endosulfan; pyrethroids;carbamates; insecticidal ureas; and biological agents includingnucleopolyhedro viruses (NPV), members of Bacillus thuringiensis,encapsulated delta-endotoxins of Bacillus thuringiensis, and othernaturally occurring or genetically modified insecticidal viruses.

Further examples of biologically active compounds or agents with whichcompounds of this invention can be formulated are: fungicides such asacibenzolar, aldimorph, amisulbrom, azaconazole, azoxystrobin,benalaxyl, benomyl, benthiavalicarb, benthiavalicarb-isopropyl,binomial, biphenyl, bitertanol, blasticidin-S, Bordeaux mixture(Tribasic copper sulfate), boscalid/nicobifen, bromuconazole,bupirimate, buthiobate, carboxin, carpropamid, captafol, captan,carbendazim, chloroneb, chlorothalonil, chlozolinate, clotrimazole,copper oxychloride, copper salts such as copper sulfate and copperhydroxide, cyazofamid, cyflunamid, cymoxanil, cyproconazole, cyprodinil,dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb,difenoconazole, dimethomorph, dimoxystrobin, diniconazole,diniconazole-M, dinocap, discostrobin, dithianon, dodemorph, dodine,econazole, etaconazole, edifenphos, epoxiconazole, ethaboxam, ethirimol,ethridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole,fencaramid, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferfurazoate,ferimzone, fluazinam, fludioxonil, flumetover, fluopicolide,fluoxastrobin, fluquinconazole, fluquinconazole, flusilazole,flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum,fuberidazole, furalaxyl, furametapyr, hexaconazole, hymexazole,guazatine, imazalil, imibenconazole, iminoctadine, iodicarb, ipconazole,iprobenfos, iprodione, iprovalicarb, isoconazole, isoprothiolane,kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, maneb,mapanipyrin, mefenoxam, mepronil, metalaxyl, metconazole,methasulfocarb, metiram, metominostrobin/fenominostrobin, mepanipyrim,metrafenone, miconazole, myclobutanil, neo-asozin (ferricmethanearsonate), nuarimol, octhilinone, ofurace, orysastrobin,oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, paclobutrazol,penconazole, pencycuron, penthiopyrad, perfurazoate, phosphonic acid,phthalide, picobenzamid, picoxystrobin, polyoxin, probenazole,prochloraz, procymidone, propamocarb, propamocarb-hydrochloride,propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin,pryazophos, pyrifenox, pyrimethanil, pyrifenox, pyrolnitrine,pyroquilon, quinconazole, quinoxyfen, quintozene, silthiofam,simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole,techrazene, tecloftalam, tecnazene, tetraconazole, thiabendazole,thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil,tolclofos-methyl, tolyfluanid, triadimefon, triadimenol, triarimol,triazoxide, tridemorph, trimoprhamide tricyclazole, trifloxystrobin,triforine, triticonazole, uniconazole, validamycin, vinclozolin, zineb,ziram, and zoxamide; nematocides such as aldicarb, imicyafos, oxamyl andfenamiphos; bactericides such as streptomycin; acaricides such asamitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol,dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin,fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad.

In certain instances, combinations of a compound of this invention withother biologically active (particularly invertebrate pest control)compounds or agents (i.e. active ingredients) can result in agreater-than-additive (i.e. synergistic) effect. Reducing the quantityof active ingredients released in the environment while ensuringeffective pest control is always desirable. When synergism ofinvertebrate pest control active ingredients occurs at application ratesgiving agronomically satisfactory levels of invertebrate pest control,such combinations can be advantageous for reducing crop production costand decreasing environmental load.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to invertebratepests (such as Bacillus thuringiensis delta-endotoxins). Such anapplication may provide a broader spectrum of plant protection and beadvantageous for resistance management. The effect of the exogenouslyapplied invertebrate pest control compounds of this invention may besynergistic with the expressed toxin proteins.

General references for these agricultural protectants (i.e.insecticides, fungicides, nematocides, acaricides, herbicides andbiological agents) include The Pesticide Manual, 13th Edition, C. D. S.Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K.,2003 and The BioPesticide Manual, 2^(nd) Edition, L. G. Copping, Ed.,British Crop Protection Council, Farnham, Surrey, U.K., 2001.

For embodiments where one or more of these various mixing partners areused, the weight ratio of these various mixing partners (in total) tothe compound of Formula 1 is typically between about 1:3000 and about3000:1. Of note are weight ratios between about 1:300 and about 300:1(for example ratios between about 1:30 and about 30:1). One skilled inthe art can easily determine through simple experimentation thebiologically effective amounts of active ingredients necessary for thedesired spectrum of biological activity. It will be evident thatincluding these additional components may expand the spectrum ofinvertebrate pests controlled beyond the spectrum controlled by thecompound of Formula 1 alone.

In certain instances, combinations of a compound of this invention withother biologically active (particularly invertebrate pest control)compounds or agents (i.e. active ingredients) can result in agreater-than-additive (i.e. synergistic) effect. Reducing the quantityof active ingredients released in the environment while ensuringeffective pest control is always desirable. When synergism ofinvertebrate pest control active ingredients occurs at application ratesgiving agronomically satisfactory levels of invertebrate pest control,such combinations can be advantageous for reducing crop production costand decreasing environmental load.

Of note is a combination of a compound of Formula 1 with at least oneother invertebrate pest control active ingredient. Of particular note issuch a combination where the other invertebrate pest control activeingredient has a different site of action from the compound ofFormula 1. In certain instances, a combination with at least one otherinvertebrate pest control active ingredient having a similar spectrum ofcontrol but a different site of action will be particularly advantageousfor resistance management. Thus, a composition of the present inventioncan further comprise a biologically effective amount of at least oneadditional invertebrate pest control active ingredient having a similarspectrum of control but a different site of action. Contacting a plantgenetically modified to express an invertebrate pest compound (e.g.,protein) or the locus of the plant with a biologically effective amountof a compound of this invention can also provide a broader spectrum ofplant protection and be advantageous for resistance management.

Table A lists specific combinations of a compound of Formula 1 withother invertebrate pest control agents illustrative of the mixtures,compositions and methods of the present invention. The first column ofTable A lists the specific invertebrate pest control agents (e.g.,“Abamectin” in the first line). The second column of Table A lists themode of action (if known) or chemical class of the invertebrate pestcontrol agents. The third column of Table A lists embodiment(s) ofranges of weight ratios for rates at which the invertebrate pest controlagent can be applied relative to a compound of Formula 1, an N-oxide, ora salt thereof, (e.g., “50:1 to 1:50” of abamectin relative to acompound of Formula 1 by weight). Thus, for example, the first line ofTable A specifically discloses the combination of a compound of Formula1 with abamectin can be applied in a weight ratio between 50:1 to 1:50.The remaining lines of Table A are to be construed similarly. Of furthernote Table A lists specific combinations of a compound of Formula 1 withother invertebrate pest control agents illustrative of the mixtures,compositions and methods of the present invention and includesadditional embodiments of weight ratio ranges for application rates.

TABLE A Invertebrate Pest Control Agent Mode of Action or Chemical ClassTypical Weight Ratio Abamectin macrocyclic lactones 50:1 to 1:50Acetamiprid neonicotinoids 150:1 to 1:200 Amitraz octopamine receptorligands 200:1 to 1:100 Avermectin macrocyclic lactones 50:1 to 1:50Azadirachtin ecdysone agonists 100:1 to 1:120 Beta-cyfluthrin sodiumchannel modulators 150:1 to 1:200 Bifenthrin sodium channel modulators100:1 to 1:10  Buprofezin chitin synthesis inhibitors 500:1 to 1:50 Cartap nereistoxin analogs 100:1 to 1:200 Chlorantraniliprole ryanodinereceptor ligands 100:1 to 1:120 Chlorfenapyr mitochondrial electrontransport inhibitors 300:1 to 1:200 Chlorpyrifos cholinesteraseinhibitors 500:1 to 1:200 Clothianidin neonicotinoids 100:1 to 1:400Cyfluthrin sodium channel modulators 150:1 to 1:200 Cyhalothrin sodiumchannel modulators 150:1 to 1:200 Cypermethrin sodium channel modulators150:1 to 1:200 Cyromazine chitin synthesis inhibitors 400:1 to 1:50 Deltamethrin sodium channel modulators  50:1 to 1:400 Dieldrincyclodiene insecticides 200:1 to 1:100 Dinotefuran neonicotinoids 150:1to 1:200 Diofenolan molting inhibitor 150:1 to 1:200 Emamectinmacrocyclic lactones 50:1 to 1:10 Endosulfan cyclodiene insecticides200:1 to 1:100 Esfenvalerate sodium channel modulators 100:1 to 1:400Ethiprole GABA-regulated chloride channel 200:1 to 1:100 blockersFenothiocarb 150:1 to 1:200 Fenoxycarb juvenile hormone mimics 500:1 to1:100 Fenvalerate sodium channel modulators 150:1 to 1:200 FipronilGABA-regulated chloride channel 150:1 to 1:100 blockers Flonicamid 200:1to 1:100 Flubendiamide ryanodine receptor ligands 100:1 to 1:120Flufenoxuron chitin synthesis inhibitors 200:1 to 1:100 Hexaflumuronchitin synthesis inhibitors 300:1 to 1:50  Hydramethylnon mitochondrialelectron transport inhibitors 150:1 to 1:250 Imidacloprid neonicotinoids1000:1 to 1:1000 Indoxacarb sodium channel modulators 200:1 to 1:50 Lambda-cyhalothrin sodium channel modulators  50:1 to 1:250 Lufenuronchitin synthesis inhibitors 500:1 to 1:250 Metaflumizone 200:1 to 1:200Methomyl cholinesterase inhibitors 500:1 to 1:100 Methoprene juvenilehormone mimics 500:1 to 1:100 Methoxyfenozide ecdysone agonists 50:1 to1:50 Nitenpyram neonicotinoids 150:1 to 1:200 Nithiazine neonicotinoids150:1 to 1:200 Novaluron chitin synthesis inhibitors 500:1 to 1:150Oxamyl cholinesterase inhibitors 200:1 to 1:200 Pymetrozine 200:1 to1:100 Pyrethrin sodium channel modulators 100:1 to 1:10  Pyridabenmitochondrial electron transport inhibitors 200:1 to 1:100 Pyridalyl200:1 to 1:100 Pyriproxyfen juvenile hormone mimics 500:1 to 1:100Ryanodine ryanodine receptor ligands 100:1 to 1:120 Spinetorammacrocyclic lactones 150:1 to 1:100 Spinosad macrocyclic lactones 500:1to 1:10  Spirodiclofen lipid biosynthesis inhibitors 200:1 to 1:200Spiromesifen lipid biosynthesis inhibitors 200:1 to 1:200 Tebufenozideecdysone agonists 500:1 to 1:250 Thiacloprid neonicotinoids 100:1 to1:200 Thiamethoxam neonicotinoids 1250:1 to 1:1000 Thiodicarbcholinesterase inhibitors 500:1 to 1:400 Thiosultap-sodium 150:1 to1:100 Tralomethrin sodium channel modulators 150:1 to 1:200 Triazamatecholinesterase inhibitors 250:1 to 1:100 Triflumuron chitin synthesisinhibitors 200:1 to 1:100 Bacillus thuringiensis biological agents 50:1to 1:10 Bacillus thuringiensis biological agents 50:1 to 1:10delta-endotoxin NPV (e.g., Gemstar) biological agents 50:1 to 1:10

The weight ratios of a compound, including a compound of Formula 1, anN-oxide or a salt thereof, to the additional invertebrate pest controlagent typically are between 1000:1 and 1:1000, with one embodiment beingbetween 500:1 and 1:500, another embodiment being between 250:1 and1:200 and another embodiment being between 100:1 and 1:50.

Listed below in Table B are embodiments of specific compositionscomprising a compound of Formula 1 (compound numbers refer to compoundsin Index Table A) and an additional invertebrate pest control agent.

TABLE B Mixture Comp. Invertebrate Pest Control No. No. and Agent A-1 66and Abamectin A-2 66 and Acetamiprid A-3 66 and Amitraz A-4 66 andAvermectin A-5 66 and Azadirachtin A-6 66 and Beta-cyfluthrin A-7 66 andBifenthrin A-8 66 and Buprofezin A-9 66 and Cartap A-10 66 andChlorantraniliprole A-11 66 and Chlorfenapyr A-12 66 and ChlorpyrifosA-13 66 and Clothianidin A-14 66 and Cyfluthrin A-15 66 and CyhalothrinA-16 66 and Cypermethrin A-17 66 and Cyromazine A-18 66 and DeltamethrinA-19 66 and Dieldrin A-20 66 and Dinotefuran A-21 66 and Diofenolan A-2266 and Emamectin A-23 66 and Endosulfan A-24 66 and Esfenvalerate A-2566 and Ethiprole A-26 66 and Fenothiocarb A-27 66 and Fenoxycarb A-28 66and Fenvalerate A-29 66 and Fipronil A-30 66 and Flonicamid A-31 66 andFlubendiamide A-32 66 and Flufenoxuron A-33 66 and Hexaflumuron A-34 66and Hydramethylnon A-35 66 and Imidacloprid A-36 66 and Indoxacarb A-3766 and Lambda-cyhalothrin A-38 66 and Lufenuron A-39 66 andMetaflumizone A-40 66 and Methomyl A-41 66 and Methoprene A-42 66 andMethoxyfenozide A-43 66 and Nitenpyram A-44 66 and Nithiazine A-45 66and Novaluron A-46 66 and Oxamyl A-47 66 and Pymetrozine A-48 66 andPyrethrin A-49 66 and Pyridaben A-50 66 and Pyridalyl A-51 66 andPyriproxyfen A-52 66 and Ryanodine A-53 66 and Spinetoram A-54 66 andSpinosad A-55 66 and Spirodiclofen A-56 66 and Spiromesifen A-57 66 andTebufenozide A-58 66 and Thiacloprid A-59 66 and Thiamethoxam A-60 66and Thiodicarb A-61 66 and Thiosultap-sodium A-62 66 and TralomethrinA-63 66 and Triazamate A-64 66 and Triflumuron A-65 66 and Bacillusthuringiensis A-66 66 and Bacillus thuringiensis delta-endotoxin A-67 66and NPV (e.g., Gemstar) B-1 76 and Abamectin B-2 76 and Acetamiprid B-376 and Amitraz B-4 76 and Avermectin B-5 76 and Azadirachtin B-6 76 andBeta-cyfluthrin B-7 76 and Bifenthrin B-8 76 and Buprofezin B-9 76 andCartap B-10 76 and Chlorantraniliprole B-11 76 and Chlorfenapyr B-12 76and Chlorpyrifos B-13 76 and Clothianidin B-14 76 and Cyfluthrin B-15 76and Cyhalothrin B-16 76 and Cypermethrin B-17 76 and Cyromazine B-18 76and Deltamethrin B-19 76 and Dieldrin B-20 76 and Dinotefuran B-21 76and Diofenolan B-22 76 and Emamectin B-23 76 and Endosulfan B-24 76 andEsfenvalerate B-25 76 and Ethiprole B-26 76 and Fenothiocarb B-27 76 andFenoxycarb B-28 76 and Fenvalerate B-29 76 and Fipronil B-30 76 andFlonicamid B-31 76 and Flubendiamide B-32 76 and Flufenoxuron B-33 76and Hexaflumuron B-34 76 and Hydramethylnon B-35 76 and ImidaclopridB-36 76 and Indoxacarb B-37 76 and Lambda-cyhalothrin B-38 76 andLufenuron B-39 76 and Metaflumizone B-40 76 and Methomyl B-41 76 andMethoprene B-42 76 and Methoxyfenozide B-43 76 and Nitenpyram B-44 76and Nithiazine B-45 76 and Novaluron B-46 76 and Oxamyl B-47 76 andPymetrozine B-48 76 and Pyrethrin B-49 76 and Pyridaben B-50 76 andPyridalyl B-51 76 and Pyriproxyfen B-52 76 and Ryanodine B-53 76 andSpinetoram B-54 76 and Spinosad B-55 76 and Spirodiclofen B-56 76 andSpiromesifen B-57 76 and Tebufenozide B-58 76 and Thiacloprid B-59 76and Thiamethoxam B-60 76 and Thiodicarb B-61 76 and Thiosultap-sodiumB-62 76 and Tralomethrin B-63 76 and Triazamate B-64 76 and TriflumuronB-65 76 and Bacillus thuringiensis B-66 76 and Bacillus thuringiensisdelta-endotoxin B-67 76 and NPV (e.g., Gemstar)

The specific mixtures listed in Table B typically combine a compound ofFormula 1 with the other invertebrate pest agent in the ratios specifiedin Table A.

Invertebrate pests are controlled in agronomic and nonagronomicapplications by applying one or more compounds of this invention,typically in the form of a composition, in a biologically effectiveamount, to the environment of the pests, including the agronomic and/ornonagronomic locus of infestation, to the area to be protected, ordirectly on the pests to be controlled.

Thus the present invention comprises a method for controlling aninvertebrate pest in agronomic and/or nonagronomic applications,comprising contacting the invertebrate pest or its environment with abiologically effective amount of one or more of the compounds of theinvention, or with a composition comprising at least one such compoundor a composition comprising at least one such compound and abiologically effective amount of at least one additional biologicallyactive compound or agent. Examples of suitable compositions comprising acompound of the invention and a biologically effective amount of atleast one additional biologically active compound or agent includegranular compositions wherein the additional active compound is presenton the same granule as the compound of the invention or on granulesseparate from those of the compound of the invention.

To achieve contact with a compound or composition of the invention toprotect a field crop from invertebrate pests, the compound orcomposition is typically applied to the seed of the crop beforeplanting, to the foliage (e.g., leaves, stems, flowers, fruits) of cropplants, or to the soil or other growth medium before or after the cropis planted.

One embodiment of a method of contact is by spraying. Alternatively, agranular composition comprising a compound of the invention can beapplied to the plant foliage or the soil. Compounds of this inventioncan also be effectively delivered through plant uptake by contacting theplant with a composition comprising a compound of this invention appliedas a soil drench of a liquid formulation, a granular formulation to thesoil, a nursery box treatment or a dip of transplants. Of note is acomposition of the present invention in the form of a soil drench liquidformulation. Also of note is a method for controlling an invertebratepest comprising contacting the invertebrate pest or its environment witha biologically effective amount of a compound of the present inventionor with a composition comprising a biologically effective amount of acompound of the present invention. Of further note is this methodwherein the environment is soil and the composition is applied to thesoil as a soil drench formulation. Of further note is that compounds ofthis invention are also effective by localized application to the locusof infestation. Other methods of contact include application of acompound or a composition of the invention by direct and residualsprays, aerial sprays, gels, seed coatings, microencapsulations,systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols,dusts and many others. One embodiment of a method of contact is adimensionally stable fertilizer granule, stick or tablet comprising acompound or composition of the invention. The compounds of thisinvention can also be impregnated into materials for fabricatinginvertebrate control devices (e.g., insect netting).

Compounds of this invention are also useful in seed treatments forprotecting seeds from invertebrate pests. In the context of the presentdisclosure and claims, treating a seed means contacting the seed with abiologically effective amount of a compound of this invention, which istypically formulated as a composition of the invention. This seedtreatment protects the seed from invertebrate soil pests and generallycan also protect roots and other plant parts in contact with the soil ofthe seedling developing from the germinating seed. The seed treatmentmay also provide protection of foliage by translocation of the compoundof this invention or a second active ingredient within the developingplant. Seed treatments can be applied to all types of seeds, includingthose from which plants genetically transformed to express specializedtraits will germinate. Representative examples include those expressingproteins toxic to invertebrate pests, such as Bacillus thuringiensistoxin or those expressing herbicide resistance such as glyphosateacetyltransferase, which provides resistance to glyphosate.

One method of seed treatment is by spraying or dusting the seed with acompound of the invention (i.e. as a formulated composition) beforesowing the seeds. Compositions formulated for seed treatment generallycomprise a film former or adhesive agent. Therefore typically a seedcoating composition of the present invention comprises a biologicallyeffective amount of a compound of Formula 1, an N-oxide or salt thereof,and a film former or adhesive agent. Seed can be coated by spraying aflowable suspension concentrate directly into a tumbling bed of seedsand then drying the seeds. Alternatively, other formulation types suchas wetted powders, solutions, suspoemulsions, emulsifiable concentratesand emulsions in water can be sprayed on the seed. This process isparticularly useful for applying film coatings on seeds. Various coatingmachines and processes are available to one skilled in the art. Suitableprocesses include those listed in P. Kosters et al., Seed TreatmentProgress and Prospects, 1994 BCPC Mongraph No. 57, and references listedtherein.

The treated seed typically comprises a compound of the present inventionin an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. fromabout 0.0001 to 1% by weight of the seed before treatment). A flowablesuspension formulated for seed treatment typically comprises from about0.5 to about 70% of the active ingredient, from about 0.5 to about 30%of a film-forming adhesive, from about 0.5 to about 20% of a dispersingagent, from 0 to about 5% of a thickener, from 0 to about 5% of apigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0to about 1% of a preservative, and from 0 to about 75% of a volatileliquid diluent.

The compounds of this invention can be incorporated into a baitcomposition that is consumed by an invertebrate pest or used within adevice such as a trap, bait station, and the like. Such a baitcomposition can be in the form of granules which comprise (a) activeingredients, namely a biologically effective amount of a compound ofFormula 1, an N-oxide, or salt thereof; (b) one or more food materials;optionally (c) an attractant, and optionally (d) one or more humectants.Of note are granules or bait compositions which comprise between about0.001-5% active ingredients, about 40-99% food material and/orattractant; and optionally about 0.05-10% humectants, which areeffective in controlling soil invertebrate pests at very low applicationrates, particularly at doses of active ingredient that are lethal byingestion rather than by direct contact. Some food materials canfunction both as a food source and an attractant. Food materials includecarbohydrates, proteins and lipids. Examples of food materials arevegetable flour, sugar, starches, animal fat, vegetable oil, yeastextracts and milk solids. Examples of attractants are odorants andflavorants, such as fruit or plant extracts, perfume, or other animal orplant component, pheromones or other agents known to attract a targetinvertebrate pest. Examples of humectants, i.e. moisture retainingagents, are glycols and other polyols, glycerine and sorbitol. Of noteis a bait composition (and a method utilizing such a bait composition)used to control at least one invertebrate pest selected from the groupconsisting of ants, termites and cockroaches. A device for controllingan invertebrate pest can comprise the present bait composition and ahousing adapted to receive the bait composition, wherein the housing hasat least one opening sized to permit the invertebrate pest to passthrough the opening so the invertebrate pest can gain access to the baitcomposition from a location outside the housing, and wherein the housingis further adapted to be placed in or near a locus of potential or knownactivity for the invertebrate pest.

The compounds of this invention can be applied without other adjuvants,but most often application will be of a formulation comprising one ormore active ingredients with suitable carriers, diluents, andsurfactants and possibly in combination with a food depending on thecontemplated end use. One method of application involves spraying awater dispersion or refined oil solution of a compound of the presentinvention. Combinations with spray oils, spray oil concentrations,spreader stickers, adjuvants, other solvents, and synergists such aspiperonyl butoxide often enhance compound efficacy. For nonagronomicuses such sprays can be applied from spray containers such as a can, abottle or other container, either by means of a pump or by releasing itfrom a pressurized container, e.g., a pressurized aerosol spray can.Such spray compositions can take various forms, for example, sprays,mists, foams, fumes or fog. Such spray compositions thus can furthercomprise propellants, foaming agents, etc. as the case may be. Of noteis a spray composition comprising a biologically effective amount of acompound or a composition of the present invention and a carrier. Oneembodiment of such a spray composition comprises a biologicallyeffective amount of a compound or a composition of the present inventionand a propellant. Representative propellants include, but are notlimited to, methane, ethane, propane, butane, isobutane, butene,pentane, isopentane, neopentane, pentene, hydrofluorocarbons,chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing. Ofnote is a spray composition (and a method utilizing such a spraycomposition dispensed from a spray container) used to control at leastone invertebrate pest selected from the group consisting of mosquitoes,black flies, stable flies, deer flies, horse flies, wasps, yellowjackets, hornets, ticks, spiders, ants, gnats, and the like, includingindividually or in combinations.

Nonagronomic uses refer to invertebrate pest control in the areas otherthan fields of crop plants. Nonagronomic uses of the present compoundsand compositions include control of invertebrate pests in stored grains,beans and other foodstuffs, and in textiles such as clothing andcarpets. Nonagronomic uses of the present compounds and compositionsalso include invertebrate pest control in ornamental plants, forests, inyards, along roadsides and railroad rights of way, and on turf such aslawns, golf courses and pastures. Nonagronomic uses of the presentcompounds and compositions also include invertebrate pest control inhouses and other buildings which may be occupied by humans and/orcompanion, farm, ranch, zoo or other animals. Nonagronomic uses of thepresent compounds and compositions also include the control of pestssuch as termites that can damage wood or other structural materials usedin buildings.

Nonagronomic uses of the present compounds and compositions also includeprotecting human and animal health by controlling invertebrate peststhat are parasitic or transmit infectious diseases. The controlling ofanimal parasites includes controlling external parasites that areparasitic to the surface of the body of the host animal (e.g.,shoulders, armpits, abdomen, inner part of the thighs) and internalparasites that are parasitic to the inside of the body of the hostanimal (e.g., stomach, intestine, lung, veins, under the skin, lymphatictissue). External parasitic or disease-transmitting pests include, forexample, chiggers, ticks, lice, mosquitoes, flies, mites and fleas.Internal parasites include heartworms, hookworms and helminths.Compounds and compositions of the present invention are particularlysuitable for combating external parasitic or disease-transmitting pests.Compounds and compositions of the present invention are suitable forsystemic and/or non-systemic control of infestation or infection byparasites on animals.

Compounds and compositions of the present invention are suitable forcombating parasites that infest animal subjects including those in thewild, livestock and agricultural working animals. Livestock is the termused to refer (singularly or plurally) to a domesticated animalintentionally reared in an agricultural setting to make produce such asfood or fiber, or for its labor; examples of livestock include cattle,sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, hens,turkeys, ducks and geese (e.g., raised for meat, milk, butter, eggs,fur, leather, feathers and/or wool). By combating parasites, fatalitiesand performance reduction (in terms of meat, milk, wool, skins, eggs,etc.) are reduced, so that applying a composition comprising a compoundof the present invention allows more economic and simple husbandry ofanimals.

Compounds and compositions of the present invention are especiallysuitable for combating parasites that infest companion animals and pets(e.g., dogs, cats, pet birds and aquarium fish), research andexperimental animals (e.g., hamsters, guinea pigs, rats and mice), aswell as animals raised for/in zoos, wild habitats and/or circuses.

In an embodiment of this invention, the animal is preferably avertebrate, and more preferably a mammal, avian or fish. In a particularembodiment, the animal subject is a mammal (including great apes, suchas humans). Other mammalian subjects include primates (e.g., monkeys),bovine (e.g., cattle or dairy cows), porcine (e.g., hogs or pigs), ovine(e.g., goats or sheep), equine (e.g., horses), canine (e.g., dogs),feline (e.g., house cats), camels, deer, donkeys, buffaloes, antelopes,rabbits, and rodents (e.g., guinea pigs, squirrels, rats, mice, gerbils,and hamsters). Avians include Anatidae (swans, ducks and geese),Columbidae (e.g., doves and pigeons), Phasianidae (e.g., partridges,grouse and turkeys), Thesienidae (e.g., domestic chickens), Psittacines(e.g., parakeets, macaws, and parrots), game birds, and ratites (e.g.,ostriches).

Of particular note is the embodiment wherein the animals to be protectedare domesticated dogs (i.e. Canis lupus familiaris) and domestic housecats (i.e. Felis catus).

Birds treated or protected by the inventive compounds can be associatedwith either commercial or noncommercial aviculture. These includeAnatidae, such as swans, geese, and ducks, Columbidae, such as doves anddomestic pigeons, Phasianidae, such as partridge, grouse and turkeys,Thesienidae, such as domestic chickens, and Psittacines, such asparakeets, macaws, and parrots raised for the pet or collector market,among others.

For purposes of the present invention, the term “fish” shall beunderstood to include without limitation, the Teleosti grouping of fish,i.e., teleosts. Both the Salmoniformes order (which includes theSalmonidae family) and the Perciformes order (which includes theCentrarchidae family) are contained within the Teleosti grouping.Examples of potential fish recipients include the Salmonidae,Serranidae, Sparidae, Cichlidae, and Centrarchidae, among others.

Other animals are also contemplated to benefit from the inventivemethods, including marsupials (such as kangaroos), reptiles (such asfarmed turtles), and other economically important domestic animals forwhich the inventive methods are safe and effective in treating orpreventing parasite infection or infestation.

Examples of invertebrate parasitic pests controlled by administering aparasiticidally effective amount of a compound of this invention to ananimal to be protected include ectoparasites (arthropods, acarines, etc)and endoparasites (helminths, e.g., nematodes, trematodes, cestodes,acanthocephalans, etc.).

The disease or group of diseases described generally as helminthiasis isdue to infection of an animal host with parasitic worms known ashelminths. The term “helminths” is meant to include nematodes,trematodes, cestodes and acanthocephalans. Helminthiasis is a prevalentand serious economic problem with domesticated animals such as swine,sheep, horses, cattle, goats, dogs, cats and poultry.

Among the helminths, the group of worms described as nematodes causeswidespread and at times serious infection in various species of animals.Nematodes that are contemplated to be treated by the compounds of thisinvention and by the inventive methods include, without limitation, thefollowing genera: Acanthocheilonema, Aelurostrongylus, Ancylostoma,Angiostrongylus, Ascaridia, Ascaris, Brugia, Bunostomum, Capillaria,Chabertia, Cooperia, Crenosoma, Dictyocaulus, Dioctophyme, Dipetalonema,Diphyllobothrium, Dirofilaria, Dracunculus, Enterobius, Filaroides,Haemonchus, Heterakis, Lagochilascaris, Loa, Mansonella, Muellerius,Necator, Nematodirus, Oesophagostomum, Ostertagia, Oxyuris, Parafilaria,Parascaris, Physaloptera, Protostrongylus, Setaria, Spirocerca,Stephanofilaria, Strongyloides, Strongylus, Thelazia, Toxascaris,Toxocara, Trichinella, Trichonema, Trichostrongylus, Trichuris,Uncinaria and Wuchereria.

Of the above, the most common genera of nematodes infecting the animalsreferred to above are Haemonchus, Trichostrongylus, Ostertagia,Nematodirus, Cooperia, Ascaris, Bunostomum, Oesophagostomum, Chabertia,Trichuris, Strongylus, Trichonema, Dictyocaulus, Capillaria, Heterakis,Toxocara, Ascaridia, Oxyuris, Ancylostoma, Uncinaria, Toxascaris andParascaris. Certain of these, such as Nematodirus, Cooperia andOesophagostomum attack primarily the intestinal tract while others, suchas Haemonchus and Ostertagia, are more prevalent in the stomach whileothers such as Dictyocaulus are found in the lungs. Still otherparasites may be located in other tissues such as the heart and bloodvessels, subcutaneous and lymphatic tissue and the like.

Trematodes that are contemplated to be treated by the compounds of thisinvention and by the inventive methods include, without limitation, thefollowing genera: Alaria, Fasciola, Nanophyetus, Opisthorchis,Paragonimus and Schistosoma.

Cestodes that are contemplated to be treated by the compounds of thisinvention and by the inventive methods include, without limitation, thefollowing genera: Diphyllobothrium, Diplydium, Spirometra and Taenia.

The most common genera of parasites of the gastrointestinal tract ofhumans are Ancylostoma, Necator, Ascaris, Strongyloides, Trichinella,Capillaria, Trichuris and Enterobius. Other medically important generaof parasites which are found in the blood or other tissues and organsoutside the gastrointestinal tract are the filarial worms such asWuchereria, Brugia, Onchocerca and Loa, as well as Dracunculus and extraintestinal stages of the intestinal worms Strongyloides and Trichinella.

Numerous other helminth genera and species are known to the art, and arealso contemplated to be treated by the compounds of the invention. Theseare enumerated in great detail in Textbook of Veterinary ClinicalParasitology, Volume 1, Helminths, E. J. L. Soulsby, F. A. Davis Co.,Philadelphia, Pa.; Helminths, Arthropods and Protozoa, (6^(th) Editionof Monnig's Veterinary Helminthology and Entomology), E. J. L. Soulsby,The Williams and Wilkins Co., Baltimore, Md.

The compounds of Formula 1 are effective against a number of animalectoparasites (e.g., arthropod ectoparasites of mammals and birds).

Insect and acarine pests include, e.g., biting insects such as flies andmosquitoes, mites, ticks, lice, fleas, true bugs, parasitic maggots, andthe like.

Adult flies include, e.g., the horn fly or Haematobia irritans, thehorse fly or Tabanus spp., the stable fly or Stomoxys calcitrans, theblack fly or Simulium spp., the deer fly or Chrysops spp., the louse flyor Melophagus ovinus, and the tsetse fly or Glossina spp. Parasitic flymaggots include, e.g., the bot fly (Oestrus ovis and Cuterebra spp.),the blow fly or Phaenicia spp., the screwworm or Cochliomyiahominivorax, the cattle grub or Hypoderma spp., the fleeceworm and theGastrophilus of horses. Mosquitoes include, for example, Culex spp.,Anopheles spp. and Aedes spp.

Mites include Mesostigmata spp. e.g., mesostigmatids such as the chickenmite, Dermanyssus gallinae; itch or scab mites such as Sarcoptidae spp.for example, Sarcoptes scabiei; mange mites such as Psoroptidae spp.including Chorioptes bovis and Psoroptes ovis; chiggers e.g.,Trombiculidae spp. for example the North American chigger, Trombiculaalfreddugesi.

Ticks include, e.g., soft-bodied ticks including Argasidae spp. forexample Argas spp. and Ornithodoros spp.; hard-bodied ticks includingIxodidae spp., for example Rhipicephalus sanguineus, Dermacentorvariabilis, Dermacentor andersoni, Amblyomma americanum, Ixodesscapularis and other Rhipicephalus spp. (including the former Boophilusgenera).

Lice include, e.g., sucking lice, e.g., Menopon spp. and Bovicola spp.;biting lice, e.g., Haematopinus spp., Linognathus spp. and Solenopotesspp.

Fleas include, e.g., Ctenocephalides spp., such as dog flea(Ctenocephalides canis) and cat flea (Ctenocephalides fells); Xenopsyllaspp. such as oriental rat flea (Xenopsylla cheopis); and Pulex spp. suchas human flea (Pulex irritans).

True bugs include, e.g., Cimicidae or e.g., the common bed bug (Cimexlectularius); Triatominae spp. including triatomid bugs also known askissing bugs; for example Rhodnius prolixus and Triatoma spp.

Generally, flies, fleas, lice, mosquitoes, gnats, mites, ticks andhelminths cause tremendous losses to the livestock and companion animalsectors. Arthropod parasites also are a nuisance to humans and canvector disease-causing organisms in humans and animals.

Numerous other arthropod pests and ectoparasites are known to the art,and are also contemplated to be treated by the compounds of theinvention. These are enumerated in great detail in Medical andVeterinary Entomology, D. S. Kettle, John Wiley & Sons, New York andToronto; Control of Arthropod Pests of Livestock: A Review ofTechnology, R. O. Drummand, J. E. George, and S. E. Kunz, CRC Press,Boca Raton, Fla.

It is also contemplated that the compounds and compositions of thisinvention may be effective against a number of protozoa endoparasites ofanimals, including those summarized by Table 1, as follows.

TABLE 1 Exemplary Parasitic Protozoa and Associated Human DiseasesRepresentative Human Disease Phylum Subphylum Genera or DisorderSarcomastigophora Mastigophora Leishmania Visceral, (with flagella,(Flagella) cutaneous and pseudopodia, or mucocutaneous both) InfectionTrypansoma Sleeping sickness Chagas' disease Giardia DiarrheaTrichomonas Vaginitis Sarcodina Entamoeba Dysentery, (pseudopodia) liverAbscess Dientamoeba Colitis Naegleria and Central nervous Acanthamoebasystem and corneal ulcers Babesia Babesiesis Apicomplexa PlasmodiumMalaria (apical complex) Isospora Diarrhea Sarcocystis DiarrheaCryptosporidum Diarrhea Toxoplasma Toxoplasmosis Eimeria Chickencoccidiosis Microspora Enterocytozoon Diarrhea Ciliaphora (withBalantidium Dysentery cilia) Unclassified Pneumocystis Pneumonia

In particular, the compounds of this invention are effective againstectoparasites including: flies such as Haematobia (Lyperosia) irritans(horn fly), Stomoxys calcitrans (stable fly), Simulium spp. (blackfly),Glossina spp. (tsetse flies), Hydrotaea irritans (head fly), Muscaautumnalis (face fly), Musca domestica (house fly), Morellia simplex(sweat fly), Tabanus spp. (horse fly), Hypoderma bovis, Hypodermalineatum, Lucilia sericata, Lucilia cuprina (green blowfly), Calliphoraspp. (blowfly), Protophormia spp., Oestrus ovis (nasal botfly),Culicoides spp. (midges), Hippobosca equine, Gastrophilus instestinalis,Gastrophilus haemorrhoidalis and Gastrophilus naslis; lice such asBovicola (Damalinia) bovis, Bovicola equi, Haematopinus asini, Felicolasubrostratus, Heterodoxus spiniger, Lignonathus setosus and Trichodectescanis; keds such as Melophagus ovinus; mites such as Psoroptes spp.,Sarcoptes scabei, Chorioptes bovis, Demodex equi, Cheyletiella spp.,Notoedres cati, Trombicula spp. and Otodectes cyanotis (ear mites);ticks such as Ixodes spp., Boophilus spp., Rhipicephalus spp., Amblyommaspp., Dermacentor spp., Hyalomma spp. and Haemaphysalis spp.; and fleassuch as Ctenocephalides felis (cat flea) and Ctenocephalides canis (dogflea).

Biologically active compounds or agents useful in the compositions ofthe present invention include the organophosphate pesticides. This classof pesticides has very broad activity as insecticides and, in certaininstances, anthelmintic activity. Organophosphate pesticides include,e.g., dicrotophos, terbufos, dimethoate, diazinon, disulfoton,trichlorfon, azinphos-methyl, chlorpyrifos, malathion,oxydemeton-methyl, methamidophos, acephate, ethyl parathion, methylparathion, mevinphos, phorate, carbofenthion and phosalone. It is alsocontemplated to include combinations of the inventive methods andcompounds with carbamate-type pesticides, including, e.g., carbaryl,carbofuran, aldicarb, molinate, methomyl, carbofuran, etc., as well ascombinations with the organochlorine-type pesticides. It is furthercontemplated to include combinations with biological pesticides,including repellents, the pyrethrins (as well as synthetic variationsthereof, e.g., allethrin, resmethrin, permethrin, tralomethrin), andnicotine, that is often employed as an acaricide. Other contemplatedcombinations are with miscellaneous pesticides including: Bacillusthuringiensis, chlorobenzilate, formamidines (e.g., amitraz), coppercompounds (e.g., copper hydroxide and cupric oxychloride sulfate),cyfluthrin, cypermethrin, dicofol, endosulfan, esfenvalerate,fenvalerate, lambda-cyhalothrin, methoxychlor and sulfur.

Of note are additional biologically active compounds or agents selectedfrom art-known anthelmintics, such as, for example, macrocyclic lactones(e.g., ivermectin, moxidectin, milbemycin), benzimidazoles (e.g.,albendazole, triclabendazole), salicylanilides (e.g., closantel,oxyclozanide), substituted phenols (e.g., nitroxynil), pyrimidines(e.g., pyrantel), imidazothiazoles (e.g., levamisole), cyclicdepsipeptides (e.g., emodepside), piperazine salts, nitroscanate andpraziquantel.

Other biologically active compounds or agents useful in the compositionsof the present invention can be selected from Insect Growth Regulators(IGRs) and Juvenile Hormone Analogues (JHAs) such as diflubenzuron,triflumuron, fluazuron, cyromazine, methoprene, etc., thereby providingboth initial and sustained control of parasites (at all stages of insectdevelopment, including eggs) on the animal subject, as well as withinthe environment of the animal subject.

Of note are biologically active compounds or agents useful in thecompositions of the present invention selected from the avermectin classof antiparasitic compounds. As stated above, the avermectin family ofcompounds includes very potent antiparasitic agents known to be usefulagainst a broad spectrum of endoparasites and ectoparasites in mammals.

A preferred compound for use within the scope of the present inventionis ivermectin. Ivermectin is a semi-synthetic derivative of avermectinand is generally produced as a mixture of at least 80%22,23-dihydroavermectin B_(1a) and less than 20% 22,23-dihydroavermectinB_(1b). Ivermectin is disclosed in U.S. Pat. No. 4,199,569.

Abamectin is an avermectin that is disclosed as avermectin B_(1a)/B_(1b)in U.S. Pat. No. 4,310,519. Abamectin contains at least 80% ofavermectin B_(1a) and not more than 20% of avermectin B_(1b).

Another preferred avermectin is doramectin, also known as25-cyclohexyl-avermectin B₁. The structure and preparation of doramectinis disclosed in U.S. Pat. No. 5,089,480.

Another preferred avermectin is moxidectin. Moxidectin, also known asLL-F28249 alpha, is known from U.S. Pat. No. 4,916,154.

Another preferred avermectin is selamectin. Selamectin is25-cyclohexyl-25-de(1-methylpropyl)-5-deoxy-22,23-dihydro-5-(hydroxyimino)-avermectinB₁ monosaccharide.

Milbemycin, or B41, is a substance which is isolated from thefermentation broth of a milbemycin-producing strain of Streptomyces. Themicroorganism, the fermentation conditions and the isolation proceduresare described in U.S. Pat. Nos. 3,950,360 and 3,984,564.

Emamectin (4″-deoxy-4″-epi-methylaminoavermectin B₁), which can beprepared as described in U.S. Pat. Nos. 5,288,710 and 5,399,717, is amixture of two homologues, 4″-deoxy-4″-epi-methylaminoavermectin B_(1a)and 4″-deoxy-4″-epi-methylaminoavermectin B_(1b). Preferably, a salt ofemamectin is used. Non-limiting examples of salts of emamectin which maybe used in the present invention include the salts described in U.S.Pat. No. 5,288,710, e.g., salts derived from benzoic acid, substitutedbenzoic acid, benzenesulfonic acid, citric acid, phosphoric acid,tartaric acid, maleic acid, and the like. Most preferably, the emamectinsalt used in the present invention is emamectin benzoate.

Eprinomectin is chemically known as4″-epi-acetylamino-4″-deoxy-avermectin B₁. Eprinomectin was specificallydeveloped to be used in all cattle classes and age groups. It was thefirst avermectin to show broad-spectrum activity against both endo- andecto-parasites while also leaving minimal residues in meat and milk. Ithas the additional advantage of being highly potent when deliveredtopically.

The composition of the present invention optionally comprisescombinations of one or more of the following antiparasite compounds:imidazo[1,2-b]pyridazine compounds as described by U.S. PatentApplication Publication No. 2005/0182059 A1; 1-(4-mono anddi-halomethylsulphonylphenyl)-2-acylamino-3-fluoropropanol compounds, asdescribed by U.S. Pat. No. 7,361,689; trifluoromethanesulfonanilideoxime ether derivatives, as described by U.S. Pat. No. 7,312,248; andn-[(phenyloxy)phenyl]-1,1,1-trifluoromethanesulfonamide andn-[(phenylsulfanyl)phenyl]-1,1,1-trifluoromethanesulfonamidederivatives, as described by PCT Patent Application Publication WO2006/135648.

The compositions of the present invention may also further comprise aflukicide. Suitable flukicides include, for example, triclabendazole,fenbendazole, albendazole, clorsulon and oxibendazole. It will beappreciated that the above combinations may further include combinationsof antibiotic, antiparasitic and anti-fluke active compounds.

In addition to the above combinations, it is also contemplated toprovide combinations of the inventive methods and compounds, asdescribed herein, with other animal health remedies such as traceelements, anti-inflammatories, anti-infectives, hormones, dermatologicalpreparations, including antiseptics and disinfectants, andimmunobiologicals such as vaccines and antisera for the prevention ofdisease.

For example, such antinfectives include one or more antibiotics that areoptionally co-administered during treatment using the inventivecompounds or methods, e.g., in a combined composition and/or in separatedosage forms. Art-known antibiotics suitable for this purpose include,for example, those listed herein below.

One useful antibiotic is florfenicol, also known asD-(threo)-1-(4-methylsulfonylphenyl)-2-dichloroacetamido-3-fluoro-1-propanol.Another preferred antibiotic compound isD-(threo)-1-(4-methylsulfonylphenyl)-2-difluoroacetamido-3-fluoro-1-propanol.Another useful antibiotic is thiamphenicol. Processes for themanufacture of these antibiotic compounds, and intermediates useful insuch processes, are described in U.S. Pat. Nos. 4,31,857; 4,582,918;4,973,750; 4,876,352; 5,227,494; 4,743,700; 5,567,844; 5,105,009;5,382,673; 5,352,832; and 5,663,361. Other florfenicol analogs and/orprodrugs have been disclosed and such analogs also can be used in thecompositions and methods of the present invention (see e.g., U.S. Pat.Nos. 7,041,670 and 7,153,842).

Another useful antibiotic compound is tilmicosin. Tilmicosin is amacrolide antibiotic that is chemically defined as20-dihydro-20-deoxy-20-(cis-3,5-dimethylpiperidin-1-yl)-desmycosin andis disclosed in U.S. Pat. No. 4,820,695.

Another useful antibiotic for use in the present invention istulathromycin. Tulathromycin may be prepared in accordance with theprocedures set forth in U.S. Pat. No. 6,825,327.

Further antibiotics for use in the present invention include thecephalosporins such as, for example, ceftiofur, cefquinome, etc. Theconcentration of the cephalosporin in the formulation of the presentinvention optionally varies between about 1 mg/mL to 500 mg/mL.

Another useful antibiotic includes the fluoroquinolones, such as, forexample, enrofloxacin, danofloxacin, difloxacin, orbifloxacin andmarbofloxacin. In the case of enrofloxacin, it may be administered in aconcentration of about 100 mg/mL. Danofloxacin may be present in aconcentration of about 180 mg/mL.

Other useful macrolide antibiotics include compounds from the class ofketolides, or, more specifically, the azalides. Such compounds aredescribed in, for example, U.S. Pat. Nos. 6,514,945; 6,472,371;6,270,768; 6,437,151; 6,271,255; 6,239,12; 5,958,888; 6,339,063; and6,054,434.

Other useful antibiotics include the tetracyclines, particularlychlortetracycline and oxytetracycline. Other antibiotics may includeβ-lactams such as penicillins, e.g., penicillin, ampicillin,amoxicillin, or a combination of amoxicillin with clavulanic acid orother beta lactamase inhibitors.

Nonagronomic applications in the veterinary sector are by conventionalmeans such as by enteral administration in the form of, for example,tablets, capsules, drinks, drenching preparations, granulates, pastes,boli, feed-through procedures, or suppositories; or by parenteraladministration, such as by injection (including intramuscular,subcutaneous, intravenous, intraperitoneal) or implants; by nasaladministration; by topical administration, for example, in the form ofimmersion or dipping, spraying, washing, coating with powder, orapplication to a small area of the animal, and through articles such asneck collars, ear tags, tail bands, limb bands or halters which comprisecompounds or compositions of the present invention.

Any of the compounds of the present invention, or a suitable combinationof such compounds, may be administered directly to the animal subjectand/or indirectly by applying it to the local environment in which theanimal dwells (such as bedding, enclosures, or the like). Directadministration includes contacting the skin, fur or feathers of asubject animal with the compounds, or by feeding or injecting thecompounds into the animal.

The compounds of the present invention may be administered in acontrolled release form, e.g., in a subcutaneous slow releaseformulation, or in the form of a controlled release device affixed to ananimal such as a flea collar. Collars for the controlled release of aninsecticide agent for long term protection against flea infestation in acompanion animal are art-known, and are described, for example, by U.S.Pat. Nos. 3,852,416; 4,224,901; 5,555,848; and 5,184,573.

Typically a parasiticidal composition according to the present inventioncomprises a mixture of a compound of Formula 1 with one or morepharmaceutically or veterinarily acceptable carriers comprisingexcipients and auxiliaries selected with regard to the intended route ofadministration (e.g., oral, topical or parenteral administration such asinjection) and in accordance with standard practice. In addition, asuitable carrier is selected on the basis of compatibility with the oneor more active ingredients in the composition, including suchconsiderations as stability relative to pH and moisture content.Therefore of note is a composition for protecting an animal from aninvertebrate parasitic pest comprising a compound of the invention (i.e.in a parasiticidally effective amount) and at least one veterinarilyacceptable carrier.

For parenteral administration including intravenous, intramuscular andsubcutaneous injection, a compound of the present invention can beformulated in suspension, solution or emulsion in oily or aqueousvehicles, and may contain adjuncts such as suspending, stabilizingand/or dispersing agents. The compounds of the present invention mayalso be formulated for bolus injection or continuous infusion.Pharmaceutical compositions for injection include aqueous solutionspreferably in physiologically compatible buffers containing otherexcipients or auxiliaries as are known in the art of pharmaceuticalformulation. Additionally, suspensions of the active compounds may beprepared in a lipophilic vehicle. Suitable lipophilic vehicles includefatty oils such as sesame oil, synthetic fatty acid esters such as ethyloleate and triglycerides, or materials such as liposomes. Aqueousinjection suspensions may contain substances that increase the viscosityof the suspension, such as sodium carboxymethyl cellulose, sorbitol, ordextran. Formulations for injection may be presented in unit dosageform, e.g., in ampoules or in multi-dose containers. Alternatively, theactive ingredient may be in powder form for constitution with a suitablevehicle, e.g., sterile, pyrogen-free water, before use.

In addition to the formulations described supra, the compounds of thepresent invention may also be formulated as a depot preparation. Suchlong acting formulations may be administered by implantation (forexample, subcutaneously or intramuscularly) or by intramuscular orsubcutaneous injection. The compounds of the present invention may beformulated for this route of administration with suitable polymeric orhydrophobic materials (e.g., in an emulsion with a pharmacologicallyacceptable oil).

For administration by inhalation, the compounds of the present inventioncan be delivered in the form of an aerosol spray using a pressurizedpack or a nebulizer and a suitable propellant, e.g., without limitation,dichlorodifluoromethane, trichlorofluoromethane,dichlorotetrafluoroethane or carbon dioxide. In the case of apressurized aerosol, the dosage unit may be controlled by providing avalve to deliver a metered amount. Capsules and cartridges of, forexample, gelatin for use in an inhaler or insufflator may be formulatedcontaining a powder mix of the compound and a suitable powder base suchas lactose or starch.

Compounds of the present invention have been discovered to havefavorable pharmacokinetic and pharmacodynamic properties providingsystemic availability from oral administration and ingestion. Thereforeafter ingestion by the animal to be protected, parasiticidally effectiveconcentrations of compounds of the invention in the bloodstream protectthe treated animal from blood-sucking pests such as fleas, ticks andlice. Therefore of note is a composition for protecting an animal froman invertebrate parasite pest in a form for oral administration (i.e.comprising, in addition to a parasiticidally effective amount of acompound of the invention, one or more carriers selected from bindersand fillers suitable for oral administration and feed concentratecarriers).

For oral administration in the form of solutions (the most readilyavailable form for absorption), emulsions, suspensions, pastes, gels,capsules, tablets, boluses, powders, granules, rumen-retention andfeed/water/lick blocks, a compound of the present invention can beformulated with binders/fillers known in the art to be suitable for oraladministration compositions, such as sugars and sugar derivatives (e.g.,lactose, sucrose, mannitol, sorbitol), starch (e.g., maize starch, wheatstarch, rice starch, potato starch), cellulose and derivatives (e.g.,methylcellulose, carboxymethylcellulose, ethylhydroxycellulose), proteinderivatives (e.g., zein, gelatin), and synthetic polymers (e.g.,polyvinyl alcohol, polyvinylpyrrolidone). If desired, lubricants (e.g.,magnesium stearate), disintegrating agents (e.g., cross-linkedpolyvinylpyrrolidinone, agar, alginic acid) and dyes or pigments can beadded. Pastes and gels often also contain adhesives (e.g., acacia,alginic acid, bentonite, cellulose, xanthan gum, colloidal magnesiumaluminum silicate) to aid in keeping the composition in contact with theoral cavity and not being easily ejected.

A preferred embodiment is a composition formulated into a chewableand/or edible product (e.g., a chewable treat or edible tablet). Such aproduct would ideally have a taste, texture and/or aroma favored by theanimal to be protected so as to facilitate oral administration of thecompound of Formula 1.

If the parasiticidal compositions are in the form of feed concentrates,the carrier is typically selected from high-performance feed, feedcereals or protein concentrates. Such feed concentrate-containingcompositions can, in addition to the parasiticidal active ingredients,comprise additives promoting animal health or growth, improving qualityof meat from animals for slaughter or otherwise useful to animalhusbandry. These additives can include, for example, vitamins,antibiotics, chemotherapeutics, bacteriostats, fungistats, coccidiostatsand hormones.

The compounds of Formula 1 may also be formulated in rectal compositionssuch as suppositories or retention enemas, using, e.g., conventionalsuppository bases such as cocoa butter or other glycerides.

Formulations for topical administration are typically in the form of apowder, cream, suspension, spray, emulsion, foam, paste, aerosol,ointment, salve or gel. More typically a topical formulation is awater-soluble solution, which can be in the form of a concentrate thatis diluted before use. Parasiticidal compositions suitable for topicaladministration typically comprise a compound of the present inventionand one or more topically suitable carriers. In applications of aparasiticidal composition topically to the exterior of an animal as aline or spot (i.e. “spot-on” treatment), the active ingredient migratesover the surface of the animal to cover most or all of its externalsurface area. As a result, the treated animal is particularly protectedfrom invertebrate pests that feed off the epidermis of the animal suchas ticks, fleas and lice. Therefore formulations for topical localizedadministration often comprise at least one organic solvent to facilitatetransport of the active ingredient over the skin and/or penetration intothe epidermis of the animal. Carriers in such formulations includepropylene glycol, paraffins, aromatics, esters such as isopropylmyristate, glycol ethers, alcohols such as ethanol, n-propanol, 2-octyldodecanol or oleyl alcohol; solutions in esters of monocarboxylic acids,such as isopropyl myristate, isopropyl palmitate, lauric acid oxalicester, oleic acid oleyl ester, oleic acid decyl ester, hexyl laurate,oleyl oleate, decyl oleate, caproic acid esters of saturated fattyalcohols of C₁₂-C₁₈ chain length; solutions of esters of dicarboxylicacids, such as dibutyl phthalate, diisopropyl isophthalate, adipic aciddiisopropyl ester, di-n-butyl adipate or solutions of esters ofaliphatic acids, e.g., glycols. It may be advantageous for acrystallization inhibitor or a dispersant known from the pharmaceuticalor cosmetic industry also to be present.

A pour-on formulation may also be prepared for control of parasites inan animal of agricultural value. The pour-on formulations of thisinvention can be in the form of a liquid, powder, emulsion, foam, paste,aerosol, ointment, salve or gel. Typically, the pour-on formulation isliquid. These pour-on formulations can be effectively applied to sheep,cattle, goats, other ruminants, camelids, pigs and horses. The pour-onformulation is typically applied by pouring in one or several lines orin a spot-on the dorsal midline (back) or shoulder of an animal. Moretypically, the formulation is applied by pouring it along the back ofthe animal, following the spine. The formulation can also be applied tothe animal by other conventional methods, including wiping animpregnated material over at least a small area of the animal, orapplying it using a commercially available applicator, by means of asyringe, by spraying or by using a spray race. The pour-on formulationsinclude a carrier and can also include one or more additionalingredients. Examples of suitable additional ingredients are stabilizerssuch as antioxidants, spreading agents, preservatives, adhesionpromoters, active solubilisers such as oleic acid, viscosity modifiers,UV blockers or absorbers, and colourants. Surface active agents,including anionic, cationic, non-ionic and ampholytic surface activeagents, can also be included in these formulations.

The formulations of this invention typically include an antioxidant,such as BHT (butylated hydroxytoluene). The antioxidant is generallypresent in amounts of at 0.1-5% (wt/vol). Some of the formulationsrequire a solubilizer, such as oleic acid, to dissolve the active agent,particularly if spinosad is used. Common spreading agents used in thesepour-on formulations include isopropyl myristate, isopropyl palmitate,caprylic/capric acid esters of saturated C₁₂-C₁₈ fatty alcohols, oleicacid, oleyl ester, ethyl oleate, triglycerides, silicone oils anddipropylene glycol methyl ether. The pour-on formulations of thisinvention are prepared according to known techniques. When the pour-onformulation is a solution, the parasiticide/insecticide is mixed withthe carrier or vehicle, using heat and stirring if required. Auxiliaryor additional ingredients can be added to the mixture of active agentand carrier, or they can be mixed with the active agent prior to theaddition of the carrier. If the pour-on formulation is an emulsion orsuspension, the formulations can be similarly prepared using knowntechniques.

Other delivery systems for relatively hydrophobic pharmaceuticalcompounds can be employed. Liposomes and emulsions are well-knownexamples of delivery vehicles or carriers for hydrophobic drugs. Inaddition, organic solvents such as dimethylsulfoxide can be used, ifneeded.

For agronomic applications, the rate of application required foreffective control (i.e. “biologically effective amount”) will depend onsuch factors as the species of invertebrate to be controlled, the pest'slife cycle, life stage, its size, location, time of year, host crop oranimal, feeding behavior, mating behavior, ambient moisture,temperature, and the like. Under normal circumstances, application ratesof about 0.01 to 2 kg of active ingredients per hectare are sufficientto control pests in agronomic ecosystems, but as little as 0.0001kg/hectare may be sufficient or as much as 8 kg/hectare may be required.For nonagronomic applications, effective use rates will range from about1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may besufficient or as much as 150 mg/square meter may be required. Oneskilled in the art can easily determine the biologically effectiveamount necessary for the desired level of invertebrate pest control.

In general for veterinary use, a compound of Formula 1 is administeredin a parasiticidally effective amount to an animal to be protected frominvertebrate parasite pests. A parasiticidally effective amount is theamount of active ingredient needed to achieve an observable effectdiminishing the occurrence or activity of the target invertebrateparasite pest. One skilled in the art will appreciate that theparasitically effective dose can vary for the various compounds andcompositions of the present invention, the desired parasitical effectand duration, the target invertebrate pest species, the animal to beprotected, the mode of application and the like, and the amount neededto achieve a particular result can be determined through simpleexperimentation.

For oral, subcutaneous or spot-on administration to homeothermicanimals, a dose of a compound of the present invention administered atsuitable intervals typically ranges from about 0.01 mg/kg to about 100mg/kg, and preferably from about 0.01 mg/kg to about 30 mg/kg of animalbody weight. For other topical (e.g., dermal) administration, includingdips and sprays, a dose typically contains from about 0.01 ppm to about150,000 ppm, more typically from about 0.01 ppm to about 100,000 ppm,preferably from about 0.01 ppm to about 5,000 ppm, and most preferablyfrom about 0.01 ppm to about 3,000 ppm, of a compound of the presentinvention.

Suitable intervals for the administration of compounds of the presentinvention to homeothermic animals range from about daily to aboutyearly. Of note are administration intervals ranging from about weeklyto about once every 6 months. Of particular note are monthlyadministration intervals (i.e. administering the compound to the animalonce every month).

The following Tests demonstrate the control efficacy of compounds ofthis invention on specific pests. “Control efficacy” representsinhibition of invertebrate pest development (including mortality) thatcauses significantly reduced feeding. The pest control protectionafforded by the compounds is not limited, however, to these species. SeeIndex Tables A-G for compound descriptions. See Index Table H for ¹H NMRdata. For mass spectral data, the numerical value reported is themolecular weight of the highest isotopic abundance parent ion (M+1)formed by addition of H⁺ (molecular weight of 1) to the molecule,observed by mass spectrometry using atmospheric pressure chemicalionization (AP⁺). The following abbreviations are used in the IndexTables which follow: Cmpd means Compound, t is tertiary, c is cyclo, Meis methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, Bu is butyl,c-Pr is cyclopropyl, c-Pn is cyclopentyl, c-Hx is cyclohexyl, t-Bu istertiary-butyl, Ph is phenyl, OMe is methoxy, SMe is methylthio, andSO₂Me means methylsulfonyl. (R) or (S) denotes the absolute chirality ofthe asymmetric carbon center. The variable “R²” represents one or acombination of substituents as listed in the Index Tables. Theabbreviation “Ex.” stands for “Example” and is followed by a numberindicating in which example the compound is prepared.

INDEX TABLE A

m.p. (° C.) or Cmpd R² R AP⁺ (M + 1) 1 3-Cl, 5-Cl CH₂CH₂NH(C═O)O-t-Bu *2 3-Cl, 5-Cl (CH₂)₆NH(C═O)O-t-Bu * 3 3-Cl, 5-Cl (CH₂)₃NMe(C═O)O-t-Bu * 43-Cl, 5-Cl (CH₂)₃NMe(C═O)Me * 5 3-Cl, 5-Cl (S)-CH(Ph)CO₂H * 6 3-Cl, 5-ClC(Me)₂CO₂H * 7 3-Cl, 5-Cl CH₂CH₂CO₂H * 8 3-Cl, 4-Cl, 5-Cl CH₂CO₂H * 93-Br, 5-Br CH₂CO₂H * 10 3-Cl, 5-Cl SO₂Me * 11 3-Cl, 5-Cl SO₂Ph * 123-Cl, 5-Cl CH₂CO₂H * 13 3-Cl, 5-Cl CH₂CO₂Na * 14 3-Cl, 5-ClCH₂CH(Cl)CH₂CH₂CH₂Cl * 15 3-CF₃, 5-CF₃ CH₂CO₂H * 16 3-CF₃ CH(Et)CH₂OH 173-CF₃

* 18 3-CF₃

* 19 3-CF₃

* 20 3-CF₃

* 21 3-CF₃ (CH₂)₃SCH₂CF₃ 609 22 3-CF₃ (CH₂)₃SCH₂CF₃ 594 23 3-Br, 5-CF₃CH₂CO₂H * 24 3-CF₃

629 25 3-CF₃, 5-CF₃ CH₂C(═O)ON═C(CH₃)₂ * 26 3-Cl, 5-CF₃ CH₂CO₂H * 273-CF₃, 5-CF₃

* 28 3-F, 5-F CH₂CO₂H 187-190 29 3-F CH₂CO₂H 182-184 30 3-Br CH₂CO₂H *31 3-CF₃, 5-CF₃ CH(CH₃)COOH 118-119 32 3-Cl, 5-CF₃ (R)-CH(CH₃)COOH * 343-Cl, 5-OCF₃ CH₂CO₂H * 35 3-Cl, 5-OCF₃ (R)-CH(CH₃)COOH * 36 3-Cl,5-OCH₂CF₃ CH₂CO₂H * 37 3-Cl, 5-OCH₂CF₃ (R)-CH(CH₃)COOH * 38 3-Br, 5-CF₃(R)-CH(CH₃)COOH * 39 3-CF₃, 5-CF₃ (R)-CH(i-Pr)COOH 40 3-F, 5-CF₃(R)-CH(CH₃)COOH * 41 3-CF₃, 5-CF₃ (R)-CH(CH₃)COOH 593 88 3-Cl, 5-CF₃CH(Et)COOH * See Index Table H for ¹H NMR data.

INDEX TABLE B

Cmpd R² R¹² R¹³ R¹⁵ m.p. (° C.) 42 3-Cl, 5-Cl H H (CH₂)₃NHMe * 43 3-Cl,5-Cl CH₃ CH₃ CH₂-c-Pr * 44 (Ex. 2) 3-Cl, 5-Cl H H CH₂-c-Pr ** 45 3-Cl,5-Cl H H CH₂-2-Py * 46 3-Cl, 5-Cl H H C₆H₄-4-CF₃ * 47 (Ex. 1) 3-Cl, 5-ClH H CH₂CH₂OCH₃ ** 48 3-Cl, 5-Cl H H CH₂CH₂SCH₃ * 49 3-Cl, 4-Cl, 5-Cl H HCH₂CH₂SCH₃ * 50 3-Cl, 5-Cl H H c-Pr * 51 3-Cl, 5-Cl H H c-Hx * 52 3-Cl,5-Cl H H c-Pn * 53 3-Cl, 5-Cl H (R)-CH₃ c-Pr * 54 3-CF₃ H H c-Pr * 553-CF₃, 5-CF₃ H H c-Pr * 56 3-Br H H CH₂-c-Pr * 57 3-Br H H CH₂CH₂SCH₃ *58 3-OCF₃ H H CH₂COOH * 59 3-OCF₃ H H CH₂-2-Py * 60 3-OCF₃ H HCH₂-c-Pr * 61 3-OCF₃ H H CH₂CH₂SCH₃ * 62 3-F, 5-F H H c-Pr * 63 3-F H Hc-Pr * 64 3-CF₃, 5-CF₃ H (R)-CH₃ c-Pr * 65 3-CF₃, 5-CF₃ H (R)-CH₃ H * 663-CF₃, 5-CF₃ H (R)-CH₃ CH₂-c-Pr * 67 3-CF₃, 5-CF₃ H CH₃ c-Pr 115-116 683-CF₃, 5-CF₃ H CH₃ CH₂-c-Pr 114-115 69 3-CF₃, 5-CF₃ H CH₃ H 113-114 703-CF₃, 5-CF₃ H H H * 71 3-CF₃, 5-CF₃ H H CH₂-c-Pr * 72 3-Cl, 5-CF₃ H(R)-CH₃ c-Pr * 73 3-Cl, 5-CF₃ H (R)-CH₃ CH₂-c-Pr * 74 3-Cl, 5-CF₃ H(R)-CH₃ H * 75 3-Cl, 5-CF₃ H H c-Pr 133-134 76 3-Cl, 5-CF₃ H H CH₂-c-Pr92-93 77 3-Cl, 5-CF₃ H H H 99-100 78 3-Cl, 5-CF₃ H CH₃ c-Pr 120-121 793-Cl, 5-CF₃ H CH₃ CH₂-c-Pr 94-95 80 3-CF₃, 5-CF₃ H (R)-CH₃

* 81 3-Cl, 5-OCF₃ H H CH₂-c-Pr * 82 3-Cl, 5-OCF₃ H H c-Pr * 83 3-Br,5-CF₃ H (R)-CH₃ H * 84 3-Cl, 5-OCH₂CF₃ H H CH₂-c-Pr * 85 3-Cl, 5-OCH₂CF₃H H c-Pr * 86 3-Cl, 5-CF₃ H (R)-Et H * 87 3-Cl, 5-CF₃ H (R)-i-Pr H * *See Index Table H for ¹H NMR data. ** See synthesis example for ¹H NMRdata.

INDEX TABLE C

Cmpd R² R¹⁴/R¹⁵ m.p. (° C.) 89 3-Cl, 5-Cl —(CH₂)₅— * 90 3-Cl, 5-Cl—(CH₂CF₂CH₂CH₂)— * 91 3-Cl, 5-Cl —(CH(CF₃)CH₂CH₂CH₂)— * 92 3-CF₃—(CH₂CH₂N(SO₂Et)CH₂CH₂)— * * See Index Table H for ¹H NMR data.

INDEX TABLE D

Cmpd R² R²⁰ q m.p. (° C.) 93 (Ex. 3) 3-Cl, 5-Cl C(═O)CF₃ 1 ** 94 (Ex. 4)3-Cl, 5-Cl H 1 ** 95 (Ex. 5) 3-Cl, 4-Cl, 5-Cl H 0 ** ** See synthesisexample for ¹H NMR data.

INDEX TABLE E

Cmpd R² R¹⁶ R¹⁷ m.p. (° C.) 96 (Ex. 6) 3-Cl, 5-Cl Me Me ** ** Seesynthesis example for ¹H NMR data.

INDEX TABLE F

Cmpd R² R m.p. (° C.)  97 3-Cl, 5-Cl (S)-CO₂CH₃ *  98 3-Cl, 5-Cl(R)-CO₂CH₃ *  99 3-Cl, 5-Cl (S)-CO₂H * 100 3-Cl, 5-Cl (R)-CO₂H * 1013-Cl, 5-Cl (S)-C(═O)NHCH₂CF₃ * 102 3-Cl, 5-Cl (R)-C(═O)NHCH₂CF₃ * 1033-Cl, 5-Cl (S)-C(═O)NHCH₃ * 104 3-Cl, 5-Cl (R)-C(═O)NHCH₃ * 105 3-Cl,5-Cl (S)-C(═O)NHCH₂CH₃ * 106 3-Cl, 5-Cl (R)-C(═O)NHCH₂CH₃ * * See IndexTable H for ¹H NMR data.

INDEX TABLE G

Cmpd R² R m.p. (° C.) 107 3-Cl, 5-Cl

* 108 3-Cl, 5-Cl

* 109 3-Cl, 5-Cl

* 110 3-CF₃, 5-CF₃

* 111 3-Cl, 5-Cl

* * See Index Table H for ¹H NMR data.

INDEX TABLE H Compound ¹H NMR Data (CDCl₃ solution unless indicatedotherwise)^(a) 1 δ 8.79 (d, 1H), 8.32 (d, 1H), 7.43-7.65 (m, 7H), 6.90(br s, 1H), 5.04 (br s, 1H), 4.25 (d, 1H), 3.89 (d, 1H), 3.64 (m, 2H),3.43 (m, 2H), 1.40 (s, 9H). 2 δ 8.80 (d, 1H), 8.25 (d, 1H), 7.45-7.66(m, 7H), 6.31 (br s, 1H), 4.56 (br s, 1H), 4.24 (d, 1H), 3.89 (d, 1H),3.52 (m, 2H), 3.11 (m, 2H), 1.40-1.69 (m, 8H), 1.40 (s, 9H). 3 δ 8.80(d, 1H), 8.35 (d, br., 1H), 7.45-7.65 (m, 8H), 4.25 (d, 1H), 3.90 (d,1H), 3.50 (m, 2H), 3.38 (m, 2H), 2.86 (s, 3H), 1.84 (m, 2H), 1.37 (s,9H). 4 δ 8.81 (d, 1H), 8.36 (d, 1H), 7.44-7.64 (m H), 4.24 (d, 1H), 3.89(d, 1H), 3.50 (m, 2H), 3.43 (m, 2H), 3.01 (s, 3H), 2.04 (s, 3H), 1.84(m, 2H). 5 δ 8.70 (m, 1H), 8.14 (m, 1H), 8.04 (br s, 1H), 7.29-7.55 (m,12H), 7.17 (m, 1H), 5.81 (d, 1H), 4.15 (d, 1H), 3.80 (d, 1H). 6 δ(CD₃C(═O)CD₃) 8.89 (d, 1H), 8.42 (d, 1H), 7.99 (br s, 1H), 7.86 (d, 1H),7.61-7.74 (m, 6H), 4.59 (d, 1H), 4.47 (d, 1H), 1.67 (s, 6H). 7 δ 8.78(d, 1H), 8.24 (d, 1H), 7.44-7.64 (m, 7H), 6.61 (t, 1H), 4.23 (d, 1H),3.87 (d, 1H), 3.80 (q, 2H), 2.77 (m, 1H). 8 δ 8.76 (d, 1H), 8.27 (d,1H), 7.68 (s, 2H), 7.59 (m, 2H), 7.54 (d, 1H), 7.40 (d, 1H), 6.74 (t,1H), 4.32 (d, 2H), 4.22 (d, 1H), 3.85 (d, 1H). 9 δ 10.41 (br s, 1H),8.71 (d, 1H), 8.20 (d, 1H), 7.48-7.75 (m, 5H), 7.44 (d, 1H), 7.31 (d,1H), 6.92 (br s, 1H), 4.26 (d, 2H), 4.17 (d, 1H), 3.83 (d, 1H). 10(CD₃S(═O)CD₃) δ 8.80 (d, 1H), 8.35 (dd, 1H), 7.95 (d, 1H), 7.80-7.90 (m,2H), 7.60-7.75 (m, 4H), 4.56 (s, 2H), 3.37 (s, 3H). 11 (CD₃C(═O)CD₃) δ8.86 (d, 1H), 8.32 (d, 1H), 8.08-8.24 (m, 2H), 7.76-7.93 (m, 4H),7.44-7.76 (m, 6H), 4.57 (d, 1H), 4.45 (d, 1H). 12 (CD₃S(═O)CD₃) δ 9.02(t, 1H), 8.81 (d, 1H), 8.37 (d, 1H), 7.92 (d, 1H), 7.83 (t, 1H),7.65-7.74 (m, 5H), 4.58 (d, 1H), 4.54 (d, 1H), 4.02 (d, 2H). 13(CD₃S(═O)CD₃) δ 8.86 (d, 1H), 8.50 (d, 1H), 7.67-7.96 (m, 8H), 4.61(apparent s, 2H), 3.64 (d, 2H). 14 δ 8.77 (d, 1H), 8.25 (d, 1H),7.40-7.64 (m, H), 6.63 (br t, 1H), 4.23 (m, 2H), 4.00 (m, 1H), 3.87 (d,1H), 3.61 (m, 3H), 1.88-2.12 (m, 4H). 15 δ 8.63 (d, 1H), 8.12 (d, 1H),8.10 (s, 2H), 7.99 (s, 1H), 7.23-7.48 (m, 4H), 6.17 (br s, 2H), 4.20 (d,1H), 4.19 (s, 2H), 3.83 (d, 1H). 16 (CD₃C(═O)CD₃) δ 8.80 (m, 1H), 8.35(m, 1H), 8.05-8.10 (m, 2H), 7.45-7.80 (m, 7H), 4.60 (d, 1H), 4.45 (d,1H), 4.13 (m, 1H), 4.0 (m, 1H), 3.67-3.72 (m, 2H), 1.77 (m, 1H), 1.60(m, 1H), 1.04 (t, 3H) 17 δ 8.82 (d, 1H), 8.21 (d, 1H), 7.83 (s, 1H),7.85 (m, 1H), 7.45-7.75 (m, 7H), 6.55-6.6 (m, 2H), 4.5 (m, 2H), 4.30 (d,1H), 4.0 (m, 2H), 3.94 (d, 1H). 18 δ 8.82 (d, 1H), 8.2 (m, 1H), 8.13 (s,1H), 7.9-7.95 (m, 2H), 7.85 (m, 1H), 7.48 (m, 1H), 7.45-7.65 (m, 5H),6.70 (br t, 1H), 4.52 (m, 2H), 4.30 (d, 1H), 3.99 (m, 2H), 3.93 (d, 1H).19 (CD₃C(═O)CD₃) δ 8.92 (d, 1H), 8.36 (d, 1H), 8.05 (s, 2H), 7.80-7.90(m, 4H), 7.6-7.7 (m, 3H), 4.65 (d, 1H), 4.48 (d, 1H), 4.40 (m, 1H), 4.13(m, 1H), 3.86 (m, 1H), 3.57-3.72 (m, 2H), 1.39 (s, 3H), 1.30 (s, 3H). 20(CD₃C(═O)CD₃) δ 8.91 (d, 1H), 8.36 (d, 1H), 8.05 (s, 2H), 7.8-7.9 (m,3H), 7.6-7.74 (m, 4H), 4.65 (d, 1H), 4.47 (d, 1H), 4.1 (m, 1H), 3.83 (m,1H), 3.70 (m, 1H), 3.49-3.63 (m, 2H), 2.0-2.1 (m, 1H), 1.85-1.95 (m,2H), 1.74 (m, 1H). 23 δ 8.81 (d, 1H), 8.33 (d, 1H), 8.02 (s, 1H), 7.87(s, 1H), 7.85 (s, 1H), 7.61-7.67 (m, 3H), 7.49 (d, 1H), 6.60 (t, 1H),4.37 (d, 2H), 4.30 (d, 1H), 3.91 (d, 1H). 25 δ 8.83 (d, 1H), 8.38 (d,1H), 8.14 (s, 2H), 8.00 (s, 1H), 7.61-7.69 (m, 3H), 7.51 (d, 1H), 6.68(br t, 1H), 4.48 (d, 2H), 4.38 (d, 1H), 3.96 (d, 1H), 2.07 (s, 3H), 2.06(s, 3H). 26 δ 8.78 (d, 1H), 8.29 (d, 1H), 7.86 (s, 1H), 7.80 (s, 1H),7.72 (s, 1H), 7.60 (m, 2H), 7.56 (d, 1H), 7.43 (d, 1H), 6.70 (br t, 1H),4.33 (d, 2H), 4.28 (d, 1H), 3.89 (d, 1H). 27 δ 8.77 (d, 1H), 8.23 (m,1H), 8.15 (s, 2H), 8.01 (s, 1H), 7.5-7.6 (m, 2H), 7.35-7.45 (m, 2H),6.63 (br t, 1H), 4.33 (d, 1H), 4.1 (m, 2H), 3.96 (d, 1H), 3.8 (m, 2H),3.4 (m, 1H), 2.05 (m, 1H), 1.9 (m, 2H), 1.65 (m, 1H). 30 (CD₃CN) δ8.79-8.88 (m, 1H), 8.32-8.41 (m, 1H), 7.89 (s, 1H), 7.61-7.77 (m, 6H),7.43-7.50 (m, 1H), 7.35 (br s, 1H), 4.43 (d, 1H), 4.14-4.22 (m, 3H). 32δ 8.78 (d, 1H), 8.28 (d, 1H), 7.86 (s, 1H), 7.80 (s, 1H), 7.72 (s, 1H),7.42-7.64 (m, 4H), 6.64 (m, 1H), 4.90 (m, 1H), 4.28 (dd, 1H), 3.89 (dd,1H), 1.62 (d, 3H). 34 δ 8.79 (d, 1H), 8.32 (d, 1H), 7.53-7.74 (m, 4H),7.40-7.51 (m, 2H), 7.34 (s, 1H), 6.64 (br s, 1H), 4.36 (d, 2H), 4.26 (d,1H), 3.88 (d, 1H). 35 δ 8.78-8.85 (m, 1H), 8.29-8.36 (m, 1H), 7.59-7.71(m, 4H), 7.50 (dd, 1H), 7.44 (s, 1H), 7.34 (s, 1H), 6.53 (d, 1H), 4.93(q, 1H), 4.27 (d, 1 H), 3.89 (d, 1H), 1.65 (d, 3H). 36 δ 9.58 (br s,1H), 8.64 (d, 1H), 8.13 (d, 1H), 7.39-7.52 (m, 2H), 7.35 (d, 1H), 7.27(s, 1H), 7.20 (d, 1H), 7.16 (s, 1H), 7.04-7.11 (m, 1H), 7.01 (t, 1H),4.40 (q, 2H), 4.19 (d, 2H), 4.11 (d, 1H), 3.78 (d, 1H). 37 δ 8.79 (s,1H), 8.31 (d, 1H), 7.55-7.71 (m, 3H), 7.47 (d, 1H), 7.32 (s, 1H), 7.20(s, 1H), 7.04 (t, 1H), 6.56 (br s, 1H), 4.92 (q, 1H), 4.41 (q, 2H), 4.23(d, 1H), 3.89 (d, 1H), 1.64 (d, 3H). 38 δ 8.74 (m, 1H), 8.24 (m, 1H),8.01 (s, 1H), 7.87 (m, 2H), 7.36-7.60 (m, 4H), 6.75 (m, 1H), 4.87 (m,1H), 4.24 (m, 1H), 3.86 (m, 1H), 1.59 (d, 3H). 40 (CD₃C(O)CD₃) δ 11.25(br s, 1H), 8.90 (d, 1H), 8.45 (d, 1H), 8.00 (br d, 1H), 7.92 (s, 1H),7.85-7.90 (m, 2H), 7.6-7.75 (m, 4H), 4.76 (m, 1H), 4.66 (d, 1H), 4.52(d, 1H), 1.56 (d, 3H). 42 (CD₃OD) δ 8.85 (d, 1H), 8.38 (d, 1H),7.57-7.78 (m, 7H), 4.44 (d, 1H), 4.19 (d, 1H), 4.08 (s, 2H), 3.38 (m,2H), 3.06 (m, 2H), 2.68 (s, 3H), 1.92 (m, 2H). 43 δ 8.82 (d, 1H), 8.29(d, 1H), 7.46-7.67 (m, 7H), 6.90 (s, 1H), 6.47 (br s, 1H), 4.26 (d, 1H),3.89 (d, 1H), 3.20 (dd, 2H), 1.79 (s, 6H), 1.01 (m, 1H), 0.55 (m, 2H),0.25 (m, 2H). 44 * 45 δ 8.82 (d, 1H), 8.52 (d, 1H), 8.34 (d, 1H),7.20-7.69 (m, 11H), 6.98 (br s, 1H), 4.61 (d, 1H), 4.32 (d, 2H), 4.26(d, 1H), 3.89 (d, 1H). 46 δ 9.35 (br s, 1H), 8.87 (d, 1H), 8.34 (d, 1H),7.44-7.71 (m, 11H), 7.35 (br s, 1H), 4.56 (d, 2H), 4.25 (d, 1H), 3.89(d, 1H). 47 * 48 δ 8.83 (d, 1H), 8.33 (d, 1H), 7.46-7.68 (m, 7H), 6.96(br s, 1H), 6.57 (br s, 1H), 4.26 (d, 1H), 4.23 (d, 2H), 3.90 (d, 1H),3.53 (q, 2H), 2.67 (t, 2H), 2.11 (s, 3H). 49 δ 8.82 (d, 1H), 8.33 (d,1H), 7.70 (s, 2H), 7.60-7.68 (m, 3H), 7.48 (d, 1H), 6.97 (br s, 1H),6.57 (br s, 1H), 4.26 (d, 1H), 4.22 (d, 2H), 3.89 (d, 1H), 3.52 (q, 2H),2.66 (t, 2H), 2.11 (s, 3H). 50 (CD₃C(═O)CD₃) δ 8.91 (d, 1H), 8.49 (d,1H), 7.63-7.88 (m, 8H), 7.41 (br s, 1H), 4.60 (d, 1H), 4.48 (d, 1H),2.76 (m, 1H), 0.67 (m, 2H), 0.49 (m, 2H). 51 δ 8.83 (d, 1H), 8.30 (d,1H), 7.46-7.66 (m, 7H), 7.12 (t, 1H), 6.25 (d, 1H), 4.25 (d, 1H), 4.18(d, 2H), 3.89 (d, 1H), 3.79 (m, 1H), 1.91 (m, 2H), 1.70 (m, 2H), 1.60(m, 1H), 1.12-1.38 (m, 5H). 52 δ 8.83 (d, 1H), 8.29 (d, 1H), 7.45-7.65(m, 7H), 7.13 (t, 1H), 6.40 (d, 1H), 4.25 (d, 1H), 4.21 (m, 1H), 4.19(d, 2H), 3.88 (d, 1H), 1.97 (m, 2H), 1.57-1.68 (m, 4H), 1.43 (m, 2H). 53δ 8.82 (d, 1H), 8.24 (d, 1H), 7.42-7.66 (m, 7H), 6.99 (br t, 1H), 6.73(br s, 1H), 4.76 (m, 1H), 4.24 (d, 1H), 3.88 (d, 1H), 2.76 (m, 1H), 1.53(d, 3H), 0.77 (m, 2H), 0.53 (m, 2H). 54 (CD₃C(═O)CD₃) δ 8.92 (d, 1H),8.50 (d, 1H), 8.06 (br s, 2H), 7.62-7.902 (m, 7H), 7.42 (br s, 1H), 4.65(d, 1H), 4.49 (d, 1H), 4.08 (d, 2H), 2.76 (m, 1H), 0.69 (m, 2H), 0.50(m, 2H). 55 (CD₃C(═O)CD₃) δ 8.92 (d, 1H), 8.50 (d, 1H), 8.38 (s, 2H),8.26 (s, 1H), 7.88 (d, 1H), 7.85 (br s, 1H), 7.75 (d, 1H), 7.64-7.72 (m,2H), 7.40 (br s, 1H), 4.74 (d, 1H), 4.65 (d, 1H), 4.08 (d, 2H), 2.76 (m,1H), 0.69 (m, 2H), 0.50 (m, 2H). 56 d 8.73-8.91 (m, 1H), 8.21-8.36 (m,1H), 7.82 (s, 1H), 7.53-7.67 (m, 5H), 7.46 (d, 1H), 7.29-7.41 (m, 1H),7.17 (t, 1H), 6.50 (br s, 1H), 4.24 (d, 1H), 4.20 (d, 2H), 3.90 (d, 1H),3.15 (dd, 2H), 0.90-1.01 (m, 1H), 0.50 (dt, 2H), 0.20 (dt, 2 H). 57 δ8.83 (d, 1H), 8.32 (d, 1H), 7.82 (s, 1H), 7.53-7.68 (m, 5H), 7.48 (d,1H), 7.30-7.41 (m, 1H), 7.04 (br s, 1H), 6.67 (br s, 1H), 4.25 (d, 1H),4.21 (d, 2H), 3.92 (d, 1H), 3.51 (dt, 2H), 2.65 (t, 2H), 2.10 (s, 3H).58 (CD₃OD) δ 8.79-8.87 (m, 1H), 8.34-8.40 (m, 1H), 7.57-7.77 (m, 7H),7.38-7.45 (m, 1H), 4.46 (d, 1H), 4.18 (d, 2H), 4.17 (d, 1H). 59 δ 8.79(d, 1H), 8.48 (d, 1H) 8.28-8.33 (m, 1H), 7.48-7.68 (m, 8H), 7.44 (d,1H), 7.29-7.35 (m, 1H), 7.14-7.26 (m, 3H), 4.56 (d, 2H), 4.22-4.31 (m,3H), 3.90 (d, 1H). 60 δ 8.81 (d, 1H), 8.24-8.31 (m, 1H), 7.48-7.64 (m,6H), 7.44 (d, 1H), 7.28-7.37 (m, 2H), 6.68 (t, 1H), 4.26 (d, 1H), 4.20(d, 2H), 3.90 (d, 1H), 3.13 (dd, 2H), 0.87-1.00 (m, 1H), 0.48 (dt, 2H),0.18 (dt, 2H). 61 δ 8.83 (d, 1H), 8.25-8.42 (m, 1H), 7.47-7.77 (m, 6H),7.32 (d, 1H), 6.95 (br s, 1H), 6.57 (br s, 1H), 4.28 (d, 1H), 4.22 (d,2H), 3.92 (d, 1H), 3.46-3.59 (m, 2H), 2.67 (d, 2H), 2.11 (s, 3H). 62 δ8.84 (d, 1H), 8.39 and 8.33 (2 d, 1H), 7.68-7.62 (m, 3H), 7.51 (d, 1H),7.23 (d, 2H), 6.99 and 6.82 (2 br s, 1H), 6.91 (t, 1H), 6.09 and 5.82 (2br s, 1H), 4.52 and 4.16 (2 d, 2H), 4.27 (d, 1H), 3.89 (d, 1H), 2.77 and2.68 (2 m, 1H), 0.83 (m, 2H), 0.71 and 0.58 (2 m 2H). 63 δ 8.85 (d, 1H),8.38 and 8.33 (2 d, 1H), 7.68-7.61 (m, 3H), 7.54-7.40 (m, 4H), 7.15 (t,1H), 6.99 and 6.83 (2 t, 1H), 6.13 and 5.82 (2 br s, 1H), 4.52 and 4.16(2 d, 2H), 4.27 (d, 1H), 3.93 (d, 1H), 2.77 and 2.63 (2 m, 1H), 0.83 (m,2H), 0.71 and 0.58 (2 m 2H). 64 δ 8.82 (m, 1H), 8.23 (m, 1H), 8.14 (s,2H), 8.00 (s, 1H), 7.40-7.66 (m, 4H), 7.08 (t, 1H), 6.81 (br s, 1H),4.78 (m, 1H), 4.34 (d, 1H), 3.92 (d, 1H), 2.76 (m, 1H), 1.53 (d, 3H),0.77 (m, 2H), 0.53 (m, 2H). 65 δ 8.81 (d, 1H), 8.25 (d, 1H), 8.14 (s,2H), 8.00 (s, 1H), 7.63 (m, 2H), 7.52 (d, 1H), 7.44 (dd, 1H), 6.95 (m,1H), 6.44 (br s, 1H), 5.65 (br s, 1H), 4.85 (m, 1H), 4.35 (d, 1H), 3.93(d, 1H), 1.57 (d, 3H). 66 δ 8.82 (d, 1H), 8.27 (d, 1H), 8.14 (s, 2H),8.00 (s, 1H), 7.42-7.66 (m, 4H), 7.02 (br s, 1H), 6.55 (br s, 1H), 4.81(m, 1H), 4.35 (d, 1H), 3.93 (d, 1H), 3.16 (m, 2H), 1.56 (d, 3H), 0.98(m, 1H), 0.50 (m, 2H), 0.21 (m, 2H). 70 δ 8.83 (d, 1H), 8.31 (d, 1H),8.13 (s, 2H), 7.99 (s, 1H), 7.68-7.61 (m, 3H), 7.49 (m, 1H), 6.85 (br s,1H), 5.99 (br s, 1H), 5.59 (br s, 1H), 4.37 (d, 1H), 4.25 (d, 2H), 3.92(d, 1H). 71 δ 8.85 (d, 1H), 8.34 (d, 1H), 8.14 (s, 2H), 8.00 (s, 1H),7.69-7.61 (m, 3H), 7.52 (d, 1H), 6.93 (br t, 1H), 6.15 (br t, 1H), 4.38(d, 1H), 4.22 (d, 2H), 3.95 (d, 1H), 3.19 (dd, 1H), 0.99 (m, 1H), 0.55(m, 2H), 0.23 (m, 2H). 72 δ 8.82 (d, 1H), 8.24 (d, 1H), 7.87 (s, 1H),7.82 (s, 1H), 7.72 (s, 1H), 7.62 (m, 2H), 7.50 (d, 1H), 7.43 (d, 1H),7.00 (br t, 1H), 6.73 (br s, 1H), 4.76 (m, 1H), 4.29 (d, 1H), 3.90 (d,1H), 2.76 (m, 1H), 0.77 (m, 2H), 0.53 (m, 2H). 73 δ 8.81 (d, 1H), 8.25(d, 1H), 7.87 (s, 1H), 7.82 (s, 1H), 7.72 (s, 1H), 7.41-7.65 (m, 4H),7.08 (br t, 1H), 6.67 (br s, 1H), 4.83 (m, 1H), 4.29 (d, 1H), 3.90 (d,1H), 3.14 (m, 2H), 1.56 (d, 3H), 0.95 (m, 1H), 0.48 (m, 2H), 0.20 (m,2H). 74 δ 8.78 (d, 1H), 8.20 (d, 1H), 7.86 (s, 1H), 7.81 (s, 1H), 7.72(s, 1H), 7.59 (m, 2H), 7.45 (d, 1H), 7.38 (d, 1H), 7.07 (m, 1H), 6.61(br s, 1H), 5.80 (s, br. 1H), 4.84 (m, 1H), 4.27 (dd, 1H), 3.88 (dd,1H), 1.54 (d, 3H). 80 δ 8.81 (d, 1H), 8.24 (d, 1H), 8.13 (s, 2H), 7.99(s, 1H), 7.43-7.67 (m, 4H), 6.94 (m, 1H), 6.80 (m, 1H), 4.82 (m, 1H),4.35 (d, 1H), 3.93 (d, 1H), 3.62 (m, 1H), 3.20 (m, 1H), 1.84 (m, 1H),1.56 (dd, 3H), 1.43 (m, 1H), 1.13 (m, 1H). 81 δ 8.77-8.88 (m, 1H),8.25-8.36 (m, 1H), 7.53-7.70 (m, 4H), 7.47 (d, 1H), 7.45 (br s, 1H),7.34 (s, 1H), 7.13 (t, 1H), 6.44 (br s, 1H), 4.27 (d, 1H), 4.21 (d, 2H),3.89 (d, 1H), 3.16 (dd, 2H), 0.89-1.02 (m, 1H), 0.51 (dt, 2H), 0.21 (dt,2H). 82 (CD₃OD) δ 8.78-8.87 (m, 1H), 8.31-8.40 (m, 1H), 7.76 (s, 1H),7.56-7.73 (m, 5H), 7.50 (s, 1H), 4.45 (d, 1H), 4.19 (d, 1H), 4.05 (s,2H), 2.65-2.75 (m, 1H), 0.70-0.78 (m, 2H), 0.50-0.58 (m, 2H). 83 δ 8.73(d, 1H), 8.15 (d, 1H), 8.01 (s, 1H), 7.85 (m, 2H), 7.22-7.57 (m, 5H),6.80 (br s, 1H), 6.03 (br s, 1H), 4.82 (m, 1H), 4.23 (m, 1H), 3.85 (m,1H), 1.50 (d, 3H). 84 δ 8.80 (d, 1H), 8.26 (d, 1H), 7.49-7.66 (m, 3H),7.40 (d, 1H), 7.36 (t, 1H), 7.31 (s, 1H), 7.16-7.23 (m, 1H), 7.03 (t,1H), 6.72 (t, 1H), 4.42 (q, 2H), 4.14-4.26 (m, 3H), 3.88 (d, 1H), 3.12(dd, 2H), 0.86-0.99 (m, 1H), 0.42-0.51 (m, 2H), 0.13-0.21 (m, 2H). 85 δ8.77-8.85 (m, 1H), 8.22-8.29 (m, 1H), 7.52-7.67 (m, 3H), 7.43 (d, 1H),7.22-7.29 (m, 1H), 7.20 (s, 1H), 7.03 (t, 1H), 6.76-6.85 (m, 1H), 4.42(q, 3H), 4.23 (d, 1H), 4.14 (d, 2H), 3.89 (d, 1H), 2.72 (dt, 1H),0.71-0.79 (m, 2H) 0.48-0.55 (m, 2H). 86 δ 8.80 (d, 1H), 8.23 (d, 1H),7.87 (s, 1H), 7.81 (s, 1H), 7.72 (s, 1H), 7.60 (m, 2H), 7.49 (d, 1H),7.42 (d, 1H), 6.97 (br d, 1H), 6.49 (br s, 1H), 5.76 (br s, 1H), 4.77(q, 1H), 4.28 (dd, 1H), 3.90 (d, 1H), 2.05 (m, 1H), 1.84 (m, 1H), 1.06(t, 3H). 87 δ 8.79 (d, 1H), 8.23 (d, 1H), 7.87 (s, 1H), 7.81 (s, 1H),7.72 (s, 1H), 7.60 (m, 2H), 7.50 (d, 1H), 7.41 (dd, 1H), 6.99 (br d,1H), 6.51 (br s, 1H), 5.86 (br s, 1H), 4.70 (dd, 1H), 4.27 (dd, 1H),3.88 (d, 1H), 2.23 (m, 1H), 1.10 (d, 3H), 1.06 (d, 3H). 89 δ 8.86 (m,1H), 8.38 (m, 1H), 7.24-7.70 (m, 8H), 4.35 (br s, 2H), 4.28 (d, 1H),3.92 (d, 1H), 3.61 (m, 2H), 3.43 (m, 2H), 1.59-1.72 (m, 6H). 90 δ 8.85(d, 1H), 8.36 (d, 1H), 7.46-7.68 (m, 7H), 7.04 (m, 1H), 4.27 (m, 2H),3.75-3.93 (m, 4H), 2.36-2.57 (m, 2H). 91 δ 8.84 (d, 1H), 8.36 (d, 1H),7.46-7.68 (m, 7H), 7.04 (br s, 1H), 4.82 (m, 1H), 4.49 (dd, 1H), 4.27(d, 2H), 3.90 (d, 1H), 3.65 (m, 2H), 2.05-2.31 (m, 4H). 92 (CD₃C(O)CD₃)δ 9.00 (m, 1H), 8.03-8.10 (m, 2H), 7.75-8.0 (m, 4H), 7.60-7.73 (m, 2H),7.54 (d, 1H), 4.65 (d, 1H), 4.48 (d, 1H), 3.9-4.05 (m, 2H), 3.45 (m,2H), 3.1-3.4 (m, 4H), 2.95-3.1 (m, 2H), 1.28 (m, 3H). 93 * 94 * 95 *96 * 97 δ 8.88 and 8.86 (2 d, 1H), 8.20 (br s, 1H), 7.67 (m, 2H),7.57-7.45 (m, 5H), 4.82 (dd, 1H), 4.28 and 4.27 (2 d, 1H), 3.91 (d, 1H),3.87 (s, 3H), 3.30 (m, 1H), 3.17 (m, 1H), 2.37, (m, 1H), 2.11 (m, 1H),1.97 (m, 1H), 1.88 (m, 1H). 98 δ 8.88 and 8.86 (2 d, 1H), 8.20 (br s,1H), 7.67 (m, 2H), 7.57-7.45 (m, 5H), 4.82 (dd, 1H), 4.28 and 4.27 (2 d,1H), 3.91 (d, 1H), 3.87 (s, 3H), 3.30 (m, 1H), 3.17 (m, 1H), 2.37, (m,1H), 2.11 (m, 1H), 1.97 (m, 1H), 1.88 (m, 1H). 99 δ 8.89 (d, 1H), 8.06(br s, 1H), 7.70-7.62 (m, 2H), 7.58-7.42 (m, 5H), 4.89 (dd, 1H), 4.8 (brs, 1H), 4.27 and 4.26 (2 d, 1H), 3.91 (d, 1H), 3.27 (m, 1H), 3.18 (m,1H), 2.34, (m, 2H), 1.99 (m, 1H), 1.88 (m, 1H). 100 δ 8.89 (d, 1H), 8.06(br s, 1H), 7.70-7.62 (m, 2H), 7.58-7.42 (m, 5H), 4.89 (dd, 1H), 4.3 (brs, 1H), 4.27 and 4.26 (2 d, 1H), 3.91 (d, 1H), 3.27 (m, 1H), 3.18 (m,1H), 2.34, (m, 2H), 1.99 (m, 1H), 1.88 (m, 1H). 101 δ 8.89 (d, 1H), 7.86(d, 1H), 7.80 (t, 1H), 7.71-7.62 (m, 2H), 7.56 (m, 3H), 7.46-7.43 (m,2H), 4.94 (dd, 1H), 4.28 and 4.27 (2 d, 1H), 4.13 (m, 1H), 3.93 (m, 1H),3.91 (d, 1H), 3.21 (m, 1H), 3.13 (m, 1H), 2.61, (m, 1H), 2.05 (m, 2H),1.86 (m, 1H). 102 δ 8.89 (d, 1H), 7.86 (d, 1H), 7.80 (t, 1H), 7.71-7.62(m, 2H), 7.56 (m, 3H), 7.46-7.43 (m, 2H), 4.94 (dd, 1H), 4.28 and 4.27(2 d, 1H), 4.13 (m, 1H), 3.93 (m, 1H), 3.91 (d, 1H), 3.21 (m, 1H), 3.13(m, 1H), 2.61, (m, 1H), 2.05 (m, 2H), 1.86 (m, 1H). 103 δ 8.89 (d, 1H),7.94 (d, 1H), 7.70-7.63 (m, 2H), 7.57-7.54 (m, 3H), 7.48-7.45 (m, 2H),7.03 (br s, 1H), 4.82 (dd, 1H), 4.29 and 4.28 (2 d, 1H), 3.91 (d, 1H),3.24 (m, 1H), 3.10 (m, 1H), 2.92 (d, 3H), 2.48, (m, 1H), 2.06 (m, 2H),1.82 (m, 1H). 104 δ 8.89 (d, 1H), 7.94 (d, 1H), 7.70-7.63 (m, 2H),7.57-7.54 (m, 3H), 7.48-7.45 (m, 2H), 7.02 (br s, 1H), 4.82 (dd, 1H),4.29 and 4.28 (2 d, 1H), 3.91 (d, 1H), 3.24 (m, 1H), 3.10 (m, 1H), 2.92(d, 3H), 2.48, (m, 1H), 2.06 (m, 2H), 1.82 (m, 1H). 105 δ 8.89 (d, 1H),7.94 (d, 1H), 7.70-7.62 (m, 2H), 7.57-7.54 (m, 3H), 7.48-7.45 (m, 2H),7.01 (br s, 1H), 4.82 (dd, 1H), 4.28 and 4.27 (2 d, 1H), 3.91 (d, 1H),3.40 (m, 2H), 3.23 (m, 1H), 3.10 (m, 1H), 2.51, (m, 1H), 2.06 (m, 2H),1.82 (m, 1H), 1.23 (t, 3H). 106 δ 8.89 (d, 1H), 7.94 (d, 1H), 7.70-7.62(m, 2H), 7.57-7.54 (m, 3H), 7.48-7.45 (m, 2H), 7.01 (br s, 1H), 4.82(dd, 1H), 4.28 and 4.27 (2 d, 1H), 3.91 (d, 1H), 3.40 (m, 2H), 3.23 (m,1H), 3.10 (m, 1H), 2.51, (m, 1H), 2.06 (m, 2H), 1.82 (m, 1H), 1.23 (t,3H). 107 δ 8.66 (br t, 1H), 8.62 (d, 1H), 8.18 (d, 1H), 7.87 (d, 1H),7.70 (dt, 1H), 7.22-7.55 (m, 7H), 4.90 (d, 2H), 4.24 (d, 1H), 3.86 (d,1H). 108 δ 8.60 (d, 1H), 7.70-7.85 (m, 5H), 7.57 (d, 2H), 7.50 (d, 1H),7.43 (t, 1H), 7.36 (d, 1H), 7.25 (dd, 1H), 4.82 (d, 2H), 4.43 (d, 1H),4.03 (d, 1H). 109 δ 8.48 (d, 1H), 7.68 (t, 1H), 7.52 (s, 2H), 7.46 (s,1H), 7.18-7.38 (m, 6H), 7.10 (s, 1H), 4.82 (d, 2H), 4.14 (d, 1H), 3.84(d, 1H), 3.76 (s, 3H). 110 δ 11.36 (s, 1H), 8.55 (s, 1H), 8.12 (s, 2H),8.00 (s, 1H), 7.58 (d, 1H), 7.43 (d, 1H), 6.32 (t, 1H), 4.39 (d, 1H),3.94 (d, 1H), 3.41 (m, 2H), 1.14 (m, 1H), 0.62 (m, 2H), 0.34 (m, 2H).111 δ 7.45-7.54 (m, 4H), 7.14-7.19 (m, 3H), 7.02 (d, 1H), 4.06-4.19 (m,3H), 3.86-3.91 (m, 1H), 3.82 & 3.77 (s, 3H), 3.27 (m, 1H), 2.98 (m, 1H),2.71 & 2.69 (s, 3H). * See synthesis example for ¹H NMR data. ^(a1)H NMRdata are in ppm downfield from tetramethylsilane. Couplings aredesignated by (s)—singlet, (d)—doublet, (t)—triplet, (q)—quartet,(dd)—doublet of doublets, (dt)—doublet of triplets, (br)—broad peaks,(m)—multiplet.

BIOLOGICAL EXAMPLES OF THE INVENTION

The following Tests demonstrate the control efficacy of compounds ofthis invention on specific pests. “Control efficacy” representsinhibition of invertebrate pest development (including mortality) thatcauses significantly reduced feeding. The pest control protectionafforded by the compounds is not limited, however, to these species. SeeIndex Tables A-G for compound descriptions.

Test A

For evaluating control of diamondback moth (Plutella xylostella) thetest unit consisted of a small open container with a 12-14-day-oldradish plant inside. This was pre-infested with about 50 neonate larvaethat were dispensed into the test unit via corn-cob grits using abazooka inoculator. The larvae moved onto the test plant after beingdispensed into the test unit.

Test compounds were formulated using a solution containing 10% acetone,90% water and 300 ppm X-77™ Spreader Lo-Foam Formula non-ionicsurfactant containing alkylarylpolyoxyethylene, free fatty acids,glycols and isopropanol (Loveland Industries, Inc. Greeley, Colo., USA).The formulated compounds were applied in 1 mL of liquid through a SUJ2atomizer nozzle with ⅛ JJ custom body (Spraying Systems Co. Wheaton,Ill., USA) positioned 1.27 cm (0.5 inches) above the top of each testunit. All experimental compounds in these tests were sprayed at 50 ppm,and the test was replicated three times. After spraying of theformulated test compound, each test unit was allowed to dry for 1 h andthen a black, screened cap was placed on top. The test units were heldfor 6 days in a growth chamber at 25° C. and 70% relative humidity.Plant feeding damage was then visually assessed based on foliageconsumed and a pest mortality rating was also counted and calculated foreach test unit.

Of the compounds of Formula 1 tested the following provided very good toexcellent levels of control efficacy (20% or less feeding damage or 80%or more mortality): 3, 4, 5, 6, 7, 8, 10, 12, 13, 14, 15, 16, 17, 18,19, 20, 21, 22, 23, 24, 25, 26, 27, 31, 32, 33, 34, 35, 37, 38, 39, 43,44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 59, 60, 62, 63,64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 76, 78, 79, 80, 81, 82, 83,84, 85, 86, 87, 89, 90, 91, 92, 93, 94, 97, 98, 99, 102, 103, 104, 105,106 and 111.

Test B

For evaluating control of fall armyworm (Spodoptera frugiperda) the testunit consisted of a small open container with a 4-5-day-old corn (maize)plant inside. This was pre-infested (using a core sampler) with 10-151-day-old larvae on a piece of insect diet. Test compounds wereformulated and sprayed at 50 ppm as described for Test A and replicatedthree times. After spraying, the test units were maintained in a growthchamber and then the control efficacy was rated for each test unit asdescribed for Test A.

Of the compounds of Formula 1 tested the following provided very good toexcellent levels of control efficacy (20% or less feeding damage or 80%or more mortality): 4, 14, 15, 16, 17, 18, 19, 20, 21, 22, 27, 31, 32,33, 38, 44, 47, 49, 50, 51, 52, 53, 54, 55, 56, 60, 64, 65, 66, 67, 68,69, 70, 71, 72, 73, 74, 76, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 90,91, 93, 94, 102, 104 and 111.

Test C

For evaluating control of potato leafhopper (Empoasca fabae) throughcontact and/or systemic means, the test unit consisted of a small opencontainer with a 5-6 day old Soleil bean plant (primary leaves emerged)inside. White sand was added to the top of the soil and one of theprimary leaves was excised prior to application. Test compounds wereformulated and sprayed as described for Test A. All experimentalcompounds in these tests were sprayed at 250 or 50 ppm as noted, and thetest was replicated three times. After spraying, the test units wereallowed to dry for 1 hour before they were post-infested with 5 potatoleafhoppers (18- to 21-day old adults). A black, screened cap was placedon the top of the cylinder. The test units were held for 6 days in agrowth chamber at 19-21° C. and 50-70% relative humidity. The controlefficacy of each test unit was then visually assessed by the insectmortality.

Of the compounds of Formula 1 tested at 250 ppm, the following providedvery good to excellent levels of control efficacy (80% or moremortality): 3, 4, 5, 6, 14, 19, 21, 22, 27, 31, 32, 43, 44, 45, 47, 48,49, 50, 53, 54, 55, 60, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 76,78, 79, 80, 90, 91, 93, 94, 103, 104 and 106.

Of the compounds of Formula 1 tested at 50 ppm, the following providedvery good to excellent levels of control efficacy (80% or moremortality): 4, 5, 6, 14, 22, 27, 31, 32, 39, 43, 44, 45, 48, 49, 50, 53,54, 55, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 76, 78, 79, 80, 81,82, 83, 86, 87, 90, 91, 93, 94, 103, 104 and 106.

Test D

For evaluating control of corn planthopper (Peregrinus maidis) throughcontact and/or systemic means, the test unit consisted of a small opencontainer with a 3-4-day-old maize plant (spike) inside. White sand wasadded to the top of the soil prior to application. Test compounds wereformulated and sprayed at 250 ppm and replicated three times asdescribed for Test A. After spraying, the test units were allowed to dryfor 1 h before they were post-infested with 10-20 corn planthoppers (18-to 20-day-old nymphs) by sprinkling them onto the sand with a saltshaker. A black, screened cap was placed on the top of the cylinder. Thetest units were held for 6 days in a growth chamber at 19-21° C. and50-70% relative humidity. Each test unit was then visually assessed forinsect mortality.

Of the compounds tested, the following resulted in at least 80%mortality: 27, 53, 72, 74, 78, 83, 86 and 91.

Test E

For evaluating control of the western flower thrips (Frankliniellaoccidentalis) through contact and/or systemic means, the test unitconsisted of a small open container with a 5-7 day old Soleil Bean plantinside. Test compounds were formulated and sprayed as described for TestA. All experimental compounds in these tests were sprayed at 250 or 50ppm as noted, and the test was replicated three times. After spraying,the test units were allowed to dry for 1 hour and then 22-27 adultthrips were added to each unit and then a black, screened cap was placedon top. The test units were held for 6 days at 25° C. and 45-55%relative humidity. A mortality rating was assessed along with a plantdamage rating for each test unit.

Of the compounds of Formula 1 tested at 250 ppm, the following providedvery good to excellent levels of control efficacy (20% or less feedingdamage or 80% or more mortality): 3, 4, 6, 8, 22, 26, 31, 33, 43, 44,45, 47, 48, 49, 50, 53, 55, 64, 66, 67, 68, 72, 73, 74, 76, 78, 79, 80,89, 90, 93, 94, 98, 104 and 106.

Of the compounds of Formula 1 tested at 50 ppm, the following providedvery good to excellent levels of control efficacy (20% or less feedingdamage or 80% or more mortality): 3, 4, 6, 22, 43, 44, 47, 50, 53, 55,64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 76, 78, 79, 80, 81, 82, 83,84, 85, 86, 87, 90, 93, 94, 104 and 106.

Test F

For evaluating control of green peach aphid (Myzus persicae) throughcontact and/or systemic means, the test unit consisted of a small opencontainer with a 12-15-day-old radish plant inside. This waspre-infested by placing on a leaf of the test plant 30-40 aphids on apiece of leaf excised from a culture plant (cut-leaf method). The larvaemoved onto the test plant as the leaf piece desiccated. Afterpre-infestation, the soil of the test unit was covered with a layer ofsand.

Test compounds were formulated and sprayed as described for Test A. Allexperimental compounds in these tests were sprayed at 250 ppm, and thetest was replicated three times. After spraying of the formulated testcompound, each test unit was allowed to dry for 1 h and then a black,screened cap was placed on top. The test units were held for 6 days in agrowth chamber at 19-21° C. and 50-70% relative humidity. Each test unitwas then visually assessed for insect mortality.

Of the compounds of Formula 1 tested, the following resulted in at least80% mortality: 4, 27, 38, 43, 44, 47, 50, 51, 53, 55, 65, 66, 67, 69,71, 72, 73, 74, 76, 78, 79, 80, 81, 82, 83, 86, 87, 90 and 93.

Test G

For evaluating control of cotton melon aphid (Aphis gossypii) throughcontact and/or systemic means, the test unit consisted of a small opencontainer with a 6-7-day-old cotton plant inside. This was pre-infestedwith 30-40 insects on a piece of leaf according to the cut-leaf methoddescribed for Test F, and the soil of the test unit was covered with alayer of sand.

Test compounds were formulated and sprayed at 250 ppm and the test wasreplicated three times. After spraying, the test units were maintainedin a growth chamber and then visually rated assessed for insectmortality.

Of the compounds tested, the following resulted in at least 80%mortality: 27, 53, 65, 71, 72, 74, 78, 82 and 83.

Test H

For evaluating control of silverleaf whitefly (Bemisia tabaci), the testunit consisted of a 14-21-day-old cotton plant grown in Redi-earth®media (Scotts Co.) with at least two true leaves infested with 2nd and3rd instar nymphs on the underside of the leaves.

Test compounds were formulated in no more than 2 mL of acetone and thendiluted with water to 25-30 mL. The formulated compounds were appliedusing a flat fan air-assisted nozzle (Spraying Systems 122440) at 10 psi(69 kPa). Plants were sprayed to run-off on a turntable sprayer (patentpublication EP-1110617-A1). All experimental compounds in this screenwere sprayed at 250 ppm and replicated three times. After spraying ofthe test compound, the test units were held for 6 days in a growthchamber at 50-60% relative humidity and 28° C. daytime and 24° C.nighttime temperature. Then the leaves were removed and then dead andlive nymphs were counted to calculate percent mortality.

Of the compounds of Formula 1 tested, the following resulted in at least80% mortality: 5, 27, 39, 73, 76, 86 and 91.

Test I

For evaluating control of the cat flea (Ctenocephalides felis), a CD-1®mouse (about 30 g, male, obtained from Charles River Laboratories,Wilmington, Mass.) was orally dosed with a test compound in an amount of10 mg/kg solubilized in propylene glycol/glycerol formal (60:40). Twohours after oral administration of the test compound, approximately 8 to16 adult fleas were applied to each mouse. The fleas were then evaluatedfor mortality 48 hours after flea application to the mouse.

Of the compounds of Formula 1 tested, the following compounds caused 50%or more mortality: 4, 21, 22, 43, 44, 47, 50, 54, 55, 64, 65, 66, 67,68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 93 and107.

TEST J

For evaluating control of the cat flea (Ctenocephalides felis Bouche), atest compound was solubilized in acetone/water (75:25) to provide afinal test concentration of 500 ppm. Then 20 μL of the 500 ppm solutionwas applied to filter paper in the bottom of a tube. The tube is allowedto dry for 3 hours. Then approximately 10 adult fleas were added to thetube and the tube was capped. The fleas were evaluated for mortality 48hours later.

Of the compounds of Formula 1 tested, the following compounds caused 50%or more mortality: 1, 3, 4, 43, 44, 47, 49, 50, 52, 65, 89 and 90.

Test K

For evaluating control of the relapsing fever tick (Ornithodorosturicata), a test compound was solubilized in propylene glycol/glycerolformal (60:40) and then diluted in bovine blood to provide a final testconcentration of 30 ppm. The treated blood was placed in a tube, and thetop of the tube was covered with a membrane. Approximately 5 O. turicatanymphs were placed on the membrane and allowed to feed on the treatedblood until fully engorged. The ticks were then evaluated for mortality48 hours later.

Of the compounds of Formula 1 tested, the following compounds caused 50%or more mortality: 43, 44, 45, 47 and 48.

What is claimed is:
 1. A compound selected from Formula 1, N-oxides andsalts thereof,

wherein A is a 6-membered aromatic ring containing carbon atoms and 0-3nitrogen atoms as ring members, said ring optionally substituted with1-5 substituents independently selected from R²;

Y⁴ is CR⁴ or N;

each W², W³, W⁴, W⁵ and W⁶ is independently O or S; L¹ is C₂-C₆ alkyleneoptionally substituted with one or more substituents independentlyselected from R²²; R¹ is C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl or C₄-C₇ cycloalkylalkyl, eachoptionally substituted with one or more substituents independentlyselected from R²¹; each R² is independently halogen, C₁-C₆ alkyl, C₁-C₆haloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, CN or NO₂; each R³ and R⁴ isindependently H, halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy,C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, CN orNO₂; R⁷ is H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₇alkylcarbonyl or C₂-C₇ alkoxycarbonyl; R⁸ is C₁-C₁₂ alkyl, C₂-C₁₂alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂ cycloalkyl, C₄-C₁₈ alkylcycloalkyl orC₄-C₁₈ cycloalkylalkyl, each substituted with one or more substituentsindependently selected from R³⁴ and optionally substituted with one ormore substituents independently selected from R³⁵; or R⁷ and R⁸ aretaken together with the nitrogen atom to which they are attached to forma ring containing as ring members in addition to the attaching nitrogenatom from 2 to 6 carbon atoms and optionally one additional ring memberselected from the group consisting of O, N and S(═O)_(u), said ringoptionally substituted with 1 to 4 substituents independently selectedfrom the group consisting of halogen, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio,C₁-C₆ haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, C(═O)R²³, CO₂R²⁴ andC(═O)NR²⁵R²⁶; each R⁹ and R¹⁸ is independently H; or C₁-C₁₂ alkyl,C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂ cycloalkyl, C₄-C₁₂alkylcycloalkyl or C₄-C₁₂ cycloalkylalkyl, each optionally substitutedwith one or more substituents independently selected from R³⁵; R¹⁰ isC₁-C₁₂ alkyl substituted with one or more R³⁵; or CN, SCN, S(═O)_(u)R³⁷,SO₂NR³⁷R³⁸, N═CR³⁸R³⁹, N═CR³⁸OR³⁹, NR³⁷C(═O)OR³⁸, NR³⁷C(═O)OR³⁸,SiR⁴¹R⁴²R⁴³, CO₂R³⁶, C(═O)R³⁶, C(═O)NR³⁷R³⁸, C(═S)SR³⁹, C(═S)OR³⁹,C(═S)R³⁸, C(═S)NR³⁷R³⁸, P(═O)(OR³⁹)₂ or P(═S)(OR³⁹)₂; provided that whenR⁹ is H or an unsubstituted group of C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl or C₄-C₇cycloalkylalkyl, then R¹⁰ is CN, SCN, S(═O)_(u)R³⁷, SO₂NR³⁷R³⁸,N═CR³⁸R³⁹, N═CR³⁸OR³⁹, SiR⁴¹R⁴²R⁴³, CO₂R³⁶, C(═O)R³⁶, C(═O)NR³⁷R³⁸,C(═S)SR³⁹, C(═S)OR³⁹, C(═S)R³⁸, C(═S)NR³⁷R³⁸, P(═O)(OR³⁹)₂ orP(═S)(OR³⁹)₂; R¹¹ is H; or C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl,C₃-C₁₂ cycloalkyl, C₄-C₁₂ alkylcycloalkyl or C₄-C₁₂ cycloalkylalkyl,each optionally substituted with one or more substituents independentlyselected from R³⁵; or CN, C(═O)R²³, CO₂R²⁴, C(═O)NR²⁵R²⁶, OR²⁷, SR²⁸,S(═O)R²⁹, SO₂R³⁰, NR³¹R³², C(═S)SR³⁷, C(═S)OR³⁷, C(═S)R³⁷, C(═S)NR³⁷R³⁸,SO₂NR³⁷R³⁸, NR³⁷C(═O)R³⁸, NR³⁷SO₂R²⁹ or Q¹; R¹² is H; or C₁-C₁₂ alkyl,C₃-C₇ cycloalkyl, C₄-C₁₂ alkylcycloalkyl, C₄-C₁₂ cycloalkylalkyl, eachoptionally substituted with one or more substituents independentlyselected from R³⁵; or Q¹; R¹³ is H; or C₁-C₁₂ alkyl, C₃-C₇ cycloalkyl,C₄-C₁₂ alkylcycloalkyl or C₄-C₁₂ cycloalkylalkyl, each optionallysubstituted with one or more substituents independently selected fromR³⁵; or CN, C(═O)R³⁶, C(═O)OR³⁷, C(═S)SR³⁷, C(═S)OR³⁷, C(═S)R³⁷,C(═S)NR³⁷R³⁸ or Q¹; or R¹² and R¹³ are taken together with the carbonatom to which they are attached to form a carbocyclic ring containing asring members from 3 to 6 carbon atoms, said ring optionally substitutedwith one or more substituents independently selected from R³⁵; R¹⁴ andR¹⁵ are independently H; or C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₂-C₁₂alkynyl, C₃-C₁₂ cycloalkyl, C₄-C₁₂ alkylcycloalkyl or C₄-C₁₂cycloalkylalkyl, each optionally substituted with one or moresubstituents independently selected from R³⁵; or CN, C(═O)R²³, CO₂R²⁴,C(═O)NR²⁵R²⁶, OR²⁷, SR²⁸, S(═O)R²⁹, SO₂R³⁰, NR³¹R³², C(═S)SR³⁷,C(═S)OR³⁷, C(═S)R³⁷, C(═S)NR³⁷R³⁸, SO₂NR³⁷R³⁸, NR³⁷C(═O)R³⁸, NR³⁷SO₂R²⁹or Q¹; or R¹⁴ and R¹⁵ are taken together with the nitrogen atom to whichthey are attached to form a ring containing as ring members in additionto the attaching nitrogen atom from 2 to 6 carbon atoms and optionallyone additional ring member selected from the group consisting of O, Nand S(═O)_(u), said ring optionally substituted with 1 to 4 substituentsindependently selected from the group consisting of halogen, C₁-C₆alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, C(═O)R²³, CO₂R²⁴, C(═O)NR²⁵R²⁶,CN and NO₂; provided that R¹⁴ and R¹⁵ are other than C₁-C₆ alkyl orC₁-C₆ haloalkyl when R¹¹ is H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl,C₂-C₇ alkylcarbonyl or C₂-C₇ alkoxycarbonyl; each R¹⁶ and R¹⁷ isindependently C₁-C₆ alkyl optionally substituted with one or moresubstituents independently selected from R³⁵; or R¹⁶ and R¹⁷ are takentogether with the sulfur atom to which they are attached to form a ringcontaining as ring members in addition to the attaching sulfur atom from3 to 6 carbon atoms, said ring optionally substituted with one or moresubstituents independently selected from R³⁵; R¹⁹ is C₁-C₆ alkyloptionally substituted with one or more substituents independentlyselected from R³⁵; R²⁰ is H; or C₁-C₆ alkyl optionally substituted withone or more substituents independently selected from R³⁵; or CN,C(═O)R²⁴, CO₂R²⁴ or NO₂; R²¹ is independently H, halogen, C₁-C₆ alkyl,C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio,C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆haloalkylsulfonyl, CN or NO₂; each R³⁵ is independently H, halogen,C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, CN, NO₂, SCN, C(═O)R³⁷, CO₂R³⁷,C(═S)SR³⁷, C(═S)OR³⁷, C(═S)R³⁷, C(═O)NR³⁷R³⁸, C(═S)NR³⁷R³⁸, SO₂NR³⁷R³⁸,NR³⁷R³⁸, SiR⁴¹R⁴²R⁴³ or Q¹; each R²³, R²⁵, R²⁶, R²⁷, R²⁸, R³¹ and R³² isindependently H; or C₁-C₁₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₉cycloalkyl, C₄-C₁₀ alkylcycloalkyl or C₄-C₁₀ cycloalkylalkyl, eachoptionally substituted with one or more substituents independentlyselected from R³⁵; or Q¹; each R²⁴, R²⁹ and R³⁰ is independently H; orC₁-C₁₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₉ cycloalkyl, C₄-C₁₀alkylcycloalkyl or C₄-C₁₀ cycloalkylalkyl, each optionally substitutedwith one or more substituents independently selected from R³⁵; or Q¹;R³⁴ is OR³⁶, OC(═O)R³⁷, OC(═O)NR³⁷R³⁸, OCO₂R³⁷, OSO₂R³⁹, SH, SR³⁶,S(═O)R³⁶, SO₂R³⁶, SO₂NR³⁷R³⁸, NR³⁶R³⁷, N═CR³⁷R⁴⁰, N═CR⁴⁰OR³⁷,NR³⁷C(═O)R³⁸, SCN, SiR⁴¹R⁴²R⁴³, CO₂H, CO₂R⁴⁶, C(═O)R⁴⁶, C(═S)SR⁴⁰,C(═S)OR⁴⁰, C(═O)SR⁴⁰, C(═S)R³⁷, C(═S)NR³⁷R³⁸, P(═O)(OR³⁷)₂ orP(═S)(OR³⁷)₂; R³⁶ is Q¹; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₇alkylcarbonyl or C₂-C₇ alkoxycarbonyl, each substituted with one or moresubstituents independently selected from halogen, CN, NO₂, OR⁴⁴, SR⁴⁴,S(═O)R⁴⁴, SO₂R⁴⁴, CO₂R⁴⁴ and C(═O)NR⁴⁴R⁴⁵; each R³⁷ and R³⁸ isindependently H; or Q¹; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₇alkylcarbonyl or C₂-C₇ alkoxycarbonyl, each optionally substituted withone of more substituents independently selected from the groupconsisting of halogen, CN, NO₂, OR⁴⁴, SR⁴⁴, S(═O)R⁴⁴, SO₂R⁴⁴, CO₂R⁴⁴,C(═O)NR⁴⁴R⁴⁵ and Q¹; R³⁹ is Q¹; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl,C₂-C₇ alkylcarbonyl or C₂-C₇ alkoxycarbonyl, each optionally substitutedwith one or more substituents independently selected from the groupconsisting of halogen, CN, NO₂, OR⁴⁴, SR⁴⁴, S(═O)R⁴⁴, SO₂R⁴⁴, CO₂R⁴⁴,C(═O)NR⁴⁴R⁴⁵ and Q¹; R⁴⁰ is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl,C₂-C₇ alkylcarbonyl, C₂-C₇ alkoxycarbonyl or a phenyl ring, eachoptionally substituted with one of more substituents independentlyselected from the group consisting of halogen, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, CN and NO₂; each R⁴¹, R⁴² and R⁴³ is independently C₁-C₆alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₄-C₇alkylcycloalkyl, C₄-C₇ cycloalkylalkyl or a phenyl ring, each optionallysubstituted with one of more substituents selected from the groupconsisting of halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl,CN and NO₂; each R⁴⁴ and R⁴⁵ is independently H; or C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl or C₄-C₇cycloalkylalkyl, each optionally substituted with one of moresubstituents selected from R³⁵; or Q¹; R⁴⁶ is Q¹; or C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇cycloalkylalkyl, C₂-C₇ alkylcarbonyl or C₂-C₇ alkoxycarbonyl, eachsubstituted with one or more substituents selected from CN, NO₂, OR⁴⁴,SR⁴⁴, S(═O)R⁴⁴, SO₂R⁴⁴, CO₂R⁴⁴ and C(═O)NR⁴⁴R⁴⁵; each Q¹ is a 3- to10-membered ring or 7- to 10-membered bicyclic ring system containing asring members from 2 to 10 carbon atoms and from 0 to 5 heteroatomsselected from the group consisting of carbon, sulfur and nitrogen atoms,of which up to two of the carbon or sulfur atoms are present as C(═O),S(═O) or SO₂, said ring or ring system optionally substituted with oneor more substituents independently selected from R²; n is an integerfrom 0 to 4; q is 0 or 1; and u is 0, 1 or
 2. 2. A compound of claim 1wherein R⁷ and R⁸ are taken together with the nitrogen atom to whichthey are attached to form a ring containing as ring members in additionto the attaching nitrogen atom from 2 to 6 carbon atoms and optionallyone additional ring member selected from the group consisting of O, Nand S(═O)_(u), said ring substituted with 1 substituent selected fromthe group consisting of CO₂R ²⁴ and C(═O)NR²⁵R²⁶.
 3. A composition forcontrolling an invertebrate pest comprising a compound of claim 1 and atleast one additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents, said compositionoptionally further comprising at least one biologically active compoundor agent in addition to said compound of claim
 1. 4. The composition ofclaim 3 wherein the at least one biologically active compound or agentis selected from the group consisting of abamectin, acephate,acequinocyl, acetamiprid, acrinathrin, amidoflumet, amitraz, avermectin,azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron,borate,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, carbofuran, cartap,chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos,chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin,cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenothiocarb,fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid,flubendiamide, flucythrinate, flufenerim, flufenoxuron, fluvalinate,tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide,hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb,insecticidal soaps, isofenphos, lufenuron, malathion, metaflumizone,metaldehyde, methamidophos, methidathion, methiodicarb, methomyl,methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide,nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion,parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon,pirimicarb, profenofos, profluthrin, propargite, protrifenbute,pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,sulprofos, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin,terbufos, tetrachlorvinphos, tetramethrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon, triflumuron, Bacillus thuringiensis delta-endotoxins,entomopathogenic bacteria, entomopathogenic viruses and entomopathogenicfungi.
 5. The composition of claim 4 wherein the at least onebiologically active compound or agent is selected from the groupconsisting of abamectin, acetamiprid, acrinathrin, amitraz, avermectin,azadirachtin, bifenthrin,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole,chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate,fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate,formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, metaflumizone, methiodicarb, methomyl,methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl,pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillusthuringiensis delta-endotoxins, all strains of Bacillus thuringiensisand all strains of Nucleo polyhydrosis viruses.
 6. A composition forcontrolling an invertebrate pest comprising a compound of claim 2 and atleast one additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents, said compositionoptionally further comprising at least one biologically active compoundor agent in addition to said compound of claim
 2. 7. The composition ofclaim 6 wherein the at least one biologically active compound or agentis selected from the group consisting of abamectin, acephate,acequinocyl, acetamiprid, acrinathrin, amidoflumet, amitraz, avermectin,azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron,borate,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, carbofuran, cartap,chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos,chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin,cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenothiocarb,fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid,flubendiamide, flucythrinate, flufenerim, flufenoxuron, fluvalinate,tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide,hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb,insecticidal soaps, isofenphos, lufenuron, malathion, metaflumizone,metaldehyde, methamidophos, methidathion, methiodicarb, methomyl,methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide,nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion,parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon,pirimicarb, profenofos, profluthrin, propargite, protrifenbute,pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,sulprofos, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin,terbufos, tetrachlorvinphos, tetramethrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon, triflumuron, Bacillus thuringiensis delta-endotoxins,entomopathogenic bacteria, entomopathogenic viruses and entomopathogenicfungi.
 8. The composition of claim 7 wherein the at least onebiologically active compound or agent is selected from the groupconsisting of abamectin, acetamiprid, acrinathrin, amitraz, avermectin,azadirachtin, bifenthrin,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole,chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate,fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate,formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, metaflumizone, methiodicarb, methomyl,methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl,pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillusthuringiensis delta-endotoxins, all strains of Bacillus thuringiensisand all strains of Nucleo polyhydrosis viruses.
 9. A compound selectedfrom Formula 1, N-oxides and salts thereof,

wherein:

W⁴ is O or S; A is a phenyl ring substituted with 1 to 3 substituentsindependently selected from the group consisting of halogen, C₁-C₃alkyl, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy and CN; R¹ is C₁-C₃ haloalkyl;each R² is independently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆haloalkylsulfonyl, CN or NO₂; each R⁴ is independently H, halogen, C₁-C₆alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, CN or NO₂; R¹¹ is H; R¹² is H orC₁-C₃ alkyl; R¹³ is H or C₁-C₃ alkyl; R¹⁴ is C₁-C₆ alkyl, C₃-C₆cycloalkyl or C₄-C₇ alkylcycloalkyl optionally substituted with one ormore substituents independently selected from R³⁵; R¹⁵ is H; or C₁-C₁₂alkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂ cycloalkyl, C₄-C₁₂alkylcycloalkyl or C₄-C₁₂ cycloalkylalkyl, each optionally substitutedwith one or more substituents independently selected from R³⁵; or CN,C(═O)R²³, CO₂R²⁴, C(═O)NR²⁵R²⁶, OR²⁷, SR²⁸, S(═O)R²⁹, SO₂R³⁰, NR³¹R³²,C(═S)SR37, C(═S)OR³⁷, C(═S)R³⁷, C(═S)NR³⁷R³⁸, SO₂NR³⁷R³⁸, NR³⁷C(═O)R³⁸,NR³⁷SO₂R²⁹ or Q¹; R³⁵ is H, halogen, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy,C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, CN orNO₂; Y⁴ is CH; each R²³, R²⁵, R²⁶, R²⁷, R²⁸, R³¹ and R³² isindependently H; or C₁-C₁₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₉cycloalkyl, C₄-C₁₀ alkylcycloalkyl or C₄-C₁₀ cycloalkylalkyl, eachoptionally substituted with one or more substituents independentlyselected from R³⁵; or Q¹; each R²⁴, R²⁹ and R³⁰ is independently H; orC₁-C₁₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₉ cycloalkyl, C₄-C₁₀alkylcycloalkyl or C₄-C₁₀ cycloalkylalkyl, each optionally substitutedwith one or more substituents independently selected from R³⁵; or Q¹;each R³⁷ and R³⁸ is independently H; or Q¹; or C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇cycloalkylalkyl, C₂-C₇ alkylcarbonyl or C₂-C₇ alkoxycarbonyl, eachoptionally substituted with one of more substituents independentlyselected from the group consisting of halogen, CN, NO₂, OR⁴⁴, SR⁴⁴,S(═O)R⁴⁴, SO₂R⁴⁴, CO₂R⁴⁴, C(═O)NR⁴⁴R⁴⁵ and Q¹; each R⁴¹, R⁴² and R⁴³ isindependently C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆cycloalkyl, C₄-C₇ alkylcycloalkyl, C₄-C₇ cycloalkylalkyl or a phenylring, each optionally substituted with one of more substituents selectedfrom the group consisting of halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ alkylsulfinyl,C₁-C₆ alkylsulfonyl, CN and NO₂; each R⁴⁴ and R⁴⁵ is independently H; orC₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₄-C₇alkylcycloalkyl or C₄-C₇ cycloalkylalkyl, each optionally substitutedwith one of more substituents selected from R³⁵; or Q¹; each Q¹ is a 3-to 10-membered ring or 7- to 10-membered bicyclic ring system containingas ring members from 2 to 10 carbon atoms and from 0 to 5 heteroatomsselected from the group consisting of carbon, sulfur and nitrogen atoms,of which up to two of the carbon or sulfur atoms are present as C(═O),S(═O) or SO₂, said ring or ring system optionally substituted with oneor more substituents independently selected from R²; and n is an integerfrom 0 to
 4. 10. A compound of claim 9 wherein: A is a phenyl ringsubstituted with 2 substituents independently selected from the groupconsisting of halogen, C₁-C₂ haloalkyl and C₁-C₂ haloalkoxy; R¹ is CF₃;R¹² is H; R¹³ is H or CH₃; R¹⁴ is cyclopropyl or methylcyclopropyloptionally substituted with one or more substituents independentlyselected from R³⁵; R¹⁵ is H; R³⁵ is H or halogen.
 11. A composition forcontrolling an invertebrate pest comprising a compound of claim 9 and atleast one additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents, said compositionoptionally further comprising at least one biologically active compoundor agent in addition to said compound of claim
 9. 12. The composition ofclaim 11 wherein the at least one biologically active compound or agentis selected from the group consisting of abamectin, acephate,acequinocyl, acetamiprid, acrinathrin, amidoflumet, amitraz, avermectin,azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron,borate,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, carbofuran, cartap,chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos,chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin,cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenothiocarb,fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid,flubendiamide, flucythrinate, flufenerim, flufenoxuron, fluvalinate,tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide,hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb,insecticidal soaps, isofenphos, lufenuron, malathion, metaflumizone,metaldehyde, methamidophos, methidathion, methiodicarb, methomyl,methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide,nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion,parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon,pirimicarb, profenofos, profluthrin, propargite, protrifenbute,pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,sulprofos, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin,terbufos, tetrachlorvinphos, tetramethrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon, triflumuron, Bacillus thuringiensis delta-endotoxins,entomopathogenic bacteria, entomopathogenic viruses and entomopathogenicfungi.
 13. The composition of claim 12 wherein the at least onebiologically active compound or agent is selected from the groupconsisting of abamectin, acetamiprid, acrinathrin, amitraz, avermectin,azadirachtin, bifenthrin,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole,chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate,fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate,formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, metaflumizone, methiodicarb, methomyl,methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl,pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillusthuringiensis delta-endotoxins, all strains of Bacillus thuringiensisand all strains of Nucleo polyhydrosis viruses.
 14. A composition forcontrolling an invertebrate pest comprising a compound of claim 10 andat least one additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents, said compositionoptionally further comprising at least one biologically active compoundor agent in addition said compound of claim
 10. 15. The composition ofclaim 14 wherein the at least one biologically active compound or agentis selected from the group consisting of abamectin, acephate,acequinocyl, acetamiprid, acrinathrin, amidoflumet, amitraz, avermectin,azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron,borate,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, carbofuran, cartap,chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos,chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin,cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenothiocarb,fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid,flubendiamide, flucythrinate, flufenerim, flufenoxuron, fluvalinate,tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide,hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb,insecticidal soaps, isofenphos, lufenuron, malathion, metaflumizone,metaldehyde, methamidophos, methidathion, methiodicarb, methomyl,methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide,nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion,parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon,pirimicarb, profenofos, profluthrin, propargite, protrifenbute,pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,sulprofos, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin,terbufos, tetrachlorvinphos, tetramethrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon, triflumuron, Bacillus thuringiensis delta-endotoxins,entomopathogenic bacteria, entomopathogenic viruses and entomopathogenicfungi.
 16. The composition of claim 15 wherein the at least onebiologically active compound or agent is selected from the groupconsisting of abamectin, acetamiprid, acrinathrin, amitraz, avermectin,azadirachtin, bifenthrin,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole,chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate,fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate,formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, metaflumizone, methiodicarb, methomyl,methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl,pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillusthuringiensis delta-endotoxins, all strains of Bacillus thuringiensisand all strains of Nucleo polyhydrosis viruses. 17.N-[2-[(cyclopropylmethyl)amino]-2-oxoethyl]-4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-Naphthalenecarboxamide.18. A composition for controlling an invertebrate pest comprising acompound of claim 17 and at least one additional component selected fromthe group consisting of surfactants, solid diluents and liquid diluents,said composition optionally further comprising at least one biologicallyactive compound or agent in addition to said compound of claim
 17. 19.The composition of claim 18 wherein the at least one biologically activecompound or agent is selected from the group consisting of abamectin,acephate, acequinocyl, acetamiprid, acrinathrin, amidoflumet, amitraz,avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate,bistrifluron, borate,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, carbofuran, cartap,chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos,chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin,cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenothiocarb,fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid,flubendiamide, flucythrinate, flufenerim, flufenoxuron, fluvalinate,tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide,hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb,insecticidal soaps, isofenphos, lufenuron, malathion, metaflumizone,metaldehyde, methamidophos, methidathion, methiodicarb, methomyl,methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide,nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion,parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon,pirimicarb, profenofos, profluthrin, propargite, protrifenbute,pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,sulprofos, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin,terbufos, tetrachlorvinphos, tetramethrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon, triflumuron, Bacillus thuringiensis delta-endotoxins,entomopathogenic bacteria, entomopathogenic viruses and entomopathogenicfungi.
 20. The composition of claim 19 wherein the at least onebiologically active compound or agent is selected from the groupconsisting of abamectin, acetamiprid, acrinathrin, amitraz, avermectin,azadirachtin, bifenthrin,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole,chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate,fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate,formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, metaflumizone, methiodicarb, methomyl,methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl,pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillusthuringiensis delta-endotoxins, all strains of Bacillus thuringiensisand all strains of Nucleo polyhydrosis viruses.
 21. A method forcontrolling an invertebrate pest comprising contacting the invertebratepest or its environment with a biologically effective amount of acompound of claim
 1. 22. A method for controlling an invertebrate pestcomprising contacting the invertebrate pest or its environment with abiologically effective amount of a compound of claim
 2. 23. A method forcontrolling an invertebrate pest comprising contacting the invertebratepest or its environment with a biologically effective amount of acompound of claim
 9. 24. A method for controlling an invertebrate pestcomprising contacting the invertebrate pest or its environment with abiologically effective amount of a compound of claim
 10. 25. A methodfor controlling an invertebrate pest comprising contacting theinvertebrate pest or its environment with a biologically effectiveamount of a compound of claim 17.